U.S. Patent Jan. 16, 2024 Sheet 18 of 19 US 11,876,211 B2

MOT laser
beams

[
Transparent

“tonization
laser

Mirror

} electrode
MOT magnets

Resistive
acceleration tube

Aperture
lon beam ee
| Deflectors
, Einzel Lens
Microchanne'!
plate detector ;
Target

FIG. 18


U.S. Patent Jan. 16, 2024 Sheet 12 of 19 US 11,876,211 B2

(A) (B)

(D)

to
I

—!
in 210

FIG. 12


US 11,876,211 B2

5

prelithiated lithium ion battery 200. Anode primer 208 can
be disposed on anode 203 such that anodic primer 208 is
interposed between anode current collector 205 and anode
203 with anode primer 208 in electrical communication with
anode 203 and anode current collector 205. Anode primer
208 can include ion beam implanted lithium 211 prior to
communication of lithium ions from anode 203 and any
other portion of prelithiated lithium ion battery 200.

Tn an embodiment, cathode 204 includes electrode par-
ticles 219; and ion beam implanted lithium 211 disposed in
electrode particles 219 prior to communication of lithium
ions from anode 203 and any other portion of prelithiated
lithium ion battery 200. According to an embodiment, anode
203 includes electrode particles 219; and ion beam
implanted lithium 211 disposed in electrode particles 219
prior to communication of lithium ions from cathode 204
and any other portion of prelithiated lithium ion battery 200.

In an embodiment, with reference to FIG. 3, prelithiated
lithium ion battery 200 includes anode 203 that includes
electrode composition 222 including electrode particles 219,
conductive additive 220, and binder 221 disposed among,
electrolyte 223; anode current collector 205 on which anode
203 is disposed; separator 206 disposed on anode 203:
cathode 204 disposed on separator 206; cathodic current

collector 207 disposed on cathode 204; and optional load 2:

224 in electrical communication with anodic current collec-
tor 205 and cathode current collector 207 and through which
electrons can flow in a reversible direction in relation to
communication of lithium ions communicated through sepa-
rator 206 from anode 203 to cathode 204 or from cathode
204 to anode 203.

In an embodiment, with reference to FIG. 4, prelithiated
lithium ion battery 200 includes anode 203 that includes
electrode composition 222 including electrode particles 219
disposed among electrolyte 223 and alteration layers of
second anodic current collector 205.2; first anodic current
collector 205.1 on which anode 203 is disposed; separator
206 disposed on anode 203; cathode 204 disposed on
separator 206; cathodic current collector 207 disposed on
cathode 204; and optional load 224 in electrical communi-
cation with first anode current collector 205.1 and cathode
current collector 207 and through which electrons can flow
in a reversible direction in relation to communication of
lithium ions communicated through separator 206 from
anode 203 to cathode 204 or from cathode 204 to anode 203.

In an embodiment, with reference to FIG. 5, prelithiated
lithium ion battery 200 includes a first current collector as
cathode current collector 207; cathode 204 on the first
current collector, cathode 204 including an interdigitated

structure that is in electrical communication with the first 5

current collector; a second current collector as anode current
collector 205; anode 203 on the second current collector,
anode 203 including a second interdigitated structure that is
in electrical communication with the second current collec-

tor, wherein anode 203 is prelithiated with ion beam s

implanted lithium that is present n anode 203 prior the SEI
formation; and an electrolyte disposed on cathode 204 and
anode 203 so that lithium ions are communicated through
the electrolyte from anode 203 to cathode 204 or from
cathode 204 to anode 203.

Tn an embodiment, prelithiated lithium ion battery 200
includes various formats such as a cylindrical format shown,
in panel A with cathode 204 and anode 203 in electrical
communication via separator 206 and disposed in battery
can 225 with terminals 226 disposed at termini of battery can
225. As shown in panel B, a prismatic format of prelithiated
lithium ion battery 200 includes cathode 204 and anode 203

20

&

&

at

6

in electrical communication via separator 206 and disposed
in battery can 225 with terminals 226 disposed on battery
can 225. As shown in panel C, a pouch format of prelithiated
lithium ion battery 200 includes a plurality of alternating
layers of cathode 204, separator 206, anode 203 disposed in
pouch 227 with terminals 226.

In an embodiment, prelithiated lithium ion battery 200
includes a cathode; an anode, ion beam implanted lithium,
and an electrolyte in electrical communication with the
cathode and the anode. The ion beam implanted lithium may
be incorporated in the cathode, incorporated in the anode,
incorporated in a separator, incorporated in current collec
tors of the battery. The ion beam implanted lithium incor-
porated in the components of the battery creates internal
sub-surface reservoirs of mobile lithium ions in an excess of
stoichiometry, which compensate for lithium losses due to
the formation of SI ‘abilize the SEI and induce controlled
solid-state amorphization and modification of the active
electrode materials by creating structural defects, dangling
bonds, diffusion channels, and connectivity pathways that
enable to facilitate ion transport and improve the perfor-
mance of the battery during electrochemical charge-dis-
charge cycling under optimized processing conditions.

In an embodiment, a process for making a prelithiated
lithium ion battery, the process comprising: disposing a first
battery member in a vacuum environment; subjecting the
first battery member to a lithium ion beam comprising
lithium ions; implanting lithium ions from the lithium ion
beam in the first battery member to prelithiate the first
battery member; disposing a second battery member on a
first battery member; disposing a third battery member on
the second battery member so that the second battery
member is interposed between the first battery member and
the third battery member to form a prelithiated battery
composite; and annealing the prelithiated battery composite
to form the prelithiated lithium ion battery such that the
prelithiated lithium ion battery has ion beam implanted
lithium that creates internal sub-surface reservoirs of mobile
lithium ions in an excess of stoichiometry, which compen-
sate for lithium losses due to the formation of the SEI,
stabilizes the SEI and induces controlled solid-state amor-
phization and modification of a portion of the first battery
member subjected to implanting the lithium ions from the
lithium ion beam by creating structural defects, dangling
bonds, diffusion channels, and pathways that enable to
facilitate ion transport and improve the performance of the
battery during electrochemical charge-discharge cycling
under optimized processing conditions.

In an embodiment, a process for making a prelithiated
lithium ion battery, the process comprising: disposing elec-
trode particles in a vacuum environment; subjecting the
electrode particles to a lithium ion beam comprising lithium
ions; implanting lithium ions from the lithium ion beam in
the electrode particles to prelithiate the electrode particles
with ion beam implanted lithium; combining, after implant-
ing lithium ions in the electrode particles, the electrode
particles with a conductive additive and a binder to form an
electrode composition; disposing, as a first electrode, the
electrode composition on a first current collector to form a
first electrode member such that the first electrode comprises
the ion beam implanted lithium that creates internal sub-
surface reservoirs of mobile lithium ions in an excess of
stoichiometry, which compensate for lithium losses due to
the formation of the SEI, stabilizes the SET and induces
controlled solid-state amorphization and modification of the
first electrode by creating structural defects, dangling bonds,
diffusion channels, and pathways that enable to facilitate ion



U.S. Patent Jan. 16, 2024 Sheet 3 of 19 US 11,876,211 B2

205

203-7

/
223 / 220 221

FIG. 3


U.S. Patent Jan. 16, 2024 Sheet 19 of 19 US 11,876,211 B2

(A) {C) + z
Li ioninay
78k

(B)

intensity (a.u.)



US 11,876,211 B2

11

conductive additive 220 can be from 1 nm to 1 cm, specifi-
cally from | um to 10 mm, and more specifically from 10 yum
to 100 pm.

Binder 221 binds together components of an electrode
(e.g., 203, 204) as a monolithic structure that can be shaped,
disposed conformally on another component such as a
current collector, or modify electrical conductivity in elec-
trodes (203, 204). Binder 221 can include acetylene black,
carbon black, graphite, carbon fibers, and carbon nanotubes,
and the like. A thickness of binder 221 can be from 1 nm to
1 om, specifically from 1 um to 10 mm, and more specifi-
cally from 10 ym to 100 um.

Electrolyte 223 provides an electrically conductive
medium to communicate Li* from anode 203 to cathode 204
or from cathode 204 to anode 203. Electrolyte 223 can be a
liquid such as lithium salts, such as LiPF,, LiBF ,LiTFSI, or
LiCl, dissolved in an organic solvent, such as ethylene
carbonate, dimethyl carbonate, and diethyl carbonate. Elec-
trolyte 223 can be polymeric, typically polyethylene oxide)
based gels or solids, also formulated similar lithium ion
salts. They can also be solid lithium metal oxides, which
allow lithium ion transport through the solid more readily
due to the intrinsic lithium content. A thickness of electrolyte
223 can be from 1 nm to 1 cm, specifically from 1 pm to 10
mm, and more specifically from 10 um to 100 um. Electro-
lyte 223 can be a condensed medium such as a solid, liquid,
glass, or gel with a selected viscosity. A viscosity of elec-
trolyte 223 can be as low as 1 centipoise for a liquid
electrolyte or completely rigid (non-viscous) in the case of
a solid electrolyte.

Prelithiated lithium ion battery 200 can be made in
various ways. In an embodiment, with reference to FIG. 1,
FIG. 2, FIG. 6, FIG. 7, FIG. 8, FIG. 9, FIG. 10, and FIG. 12,
a process for making prelithiated lithium ion battery 200
includes disposing first battery member 201 in vacuum
environment 217; subjecting first battery member 201 to
lithium ion beam 210 including ion beam implanted lithium
211; implanting ion beam implanted lithium 211 from
lithium ion beam 210 in first battery member 201 to pre-
lithiate first battery member 201; disposing second battery
member 202 on first battery member 201; disposing third
battery member 216 on second battery member 202, so that
second battery member 202 is interposed between first
battery member 201 and third battery member 216 to form
prelithiated battery composite 218; and annealing prelithi-
ated battery composite 218 to form prelithiated lithium ion
battery 200 such that prelithiated lithium ion battery 200 has
an absence of solid electrolyte interface composition in a
portion of first battery member 201 subjected to implanting
ion beam implanted lithium 211 from lithium ion beam 210.

In an embodiment, the process for making prelithiated
lithium ion battery 200 further includes, prior to disposing
second battery member 202 on first battery member 201
subjecting second battery member 202 to lithium ion beam

210; and implanting ion beam implanted lithium 211 from

lithium ion beam 210 in second battery member 202 to
prelithiate second battery member 202. According to an
embodiment, the process further includes, prior to disposing
third battery member 216 on second battery member 202:
subjecting third battery member 216 to lithium ion beam
210; and implanting ion beam implanted lithium 211 from
lithium ion beam 210 in third battery member 216 to
prelithiate second battery member 202;

In an embodiment, the process for making prelithiated
lithium ion battery 200 further includes, prior to disposing
third battery member 216 on second battery member 202:
subjecting third battery member 216 to lithium ion beam

20

3

&

&

12

210; and implanting ion beam implanted lithium 211 from
lithium ion beam 210 in third battery member 216 to
prelithiate second battery member 202.

In an embodiment, the process for making prelithiated
lithium ion battery 200, first battery member 201 includes
cathodic member 213 or anodic member 215; second battery
member 202 includes intermediate member 214; when first
battery member 201 is cathodic member 213, third battery
member 216 includes anodic member 215; and when first
battery member 201 is anodic member 215, third battery
member 216 includes cathodic member 213. In an embodi-
ment, first battery member 201 includes cathodic member
213; and third battery member 216 includes anodic member
215. According to an embodiment, first battery member 201
includes anodic member 215; and third battery member 216
includes cathodic member 213.

In an embodiment, with reference to FIG. 3 and FIG. 13,
a process for making prelithiated lithium ion battery 200
includes: disposing electrode particles 219 in vacuum envi-
ronment 217; subjecting electrode particles 219 to lithium
ion beam 210 including ion beam implanted lithium 211;
implanting ion beam implanted lithium 211 from lithium ion
beam 210 in electrode particles 219 to prelithiate electrode
particles 219 with ion beam implanted lithium: combining,

5 afier implanting ion beam implanted lithium 211 in electrode

particles 219, electrode particles 219 with conductive addi-
tive 220 and binder 221 to form an electrode composition
222; disposing, as a first electrode, electrode composition
222 on a first current collector to form a first electrode
member such that first electrode includes ion beam
implanted lithium that is present in absence of solid elec-
trolyte interface composition in first electrode; annealing the
first electrode member; and disposing the first electrode
member on a second electrode member to make prelithiated
lithium ion battery 200.

This process also can include, prior to disposing the first
electrode on the first current collector: subjecting the first
current collector to lithium ion beam 210 including ion beam,
implanted lithium 211; implanting ion beam implanted
lithium 211 from lithium ion beam 210 in the first current
collector to prelith the first current collector with ion
beam implanted lithium, wherein the first current collector
includes ion beam implanted lithium that is present in
absence of solid electrolyte interface composition in the first
current collector; and annealing the first current collector.

This process also can include, prior to disposing the first
electrode member on the second electrode member: dispos-
ing, as a second electrode, electrode composition 222 on a
second current collector to form the second electrode mem-
ber such that the second electrode includes ion beam
implanted lithium that is present in absence of solid elec-
trolyte interface composition in the second electrode; and
annealing the second electrode member.

‘The process can further include, prior to disposing the
second electrode on the second current collector: subjecting
the second current collector to lithium ion beam 210 includ-
ing ion beam implanted lithium 211; implanting ion beam
implanted lithium 211 from lithium ion beam 210 in the
second current collector to prelithiate the second current
collector with ion beam implanted lithium, wherein second
current collector includes ion beam implanted lithium that is
present in absence of solid electrolyte interface composition
in the second current collector, and annealing the first
current collector.

In an embodiment, with reference to FIG. 4 and FIG. 14,
a process for making prelithiated lithium ion battery 200
includes: forming a first current collector; forming cathode



US 11,876,211 B2

3

rectangular path in panel B, an annular path in panel C, and
an interdigitated path in panel D;
FIG. 13 shows steps in making a prelithiated lithium ion
battery using electrode particles;
FIG. 14 shows steps in making a prelithiated lithium ion
battery that includes a plurality of layers in the electrodes;
FIG. 15 shows steps in making a prelithiated lithium ion
battery that includes interdigitated anode and cathode;
FIG. 16 shows, for an ion beam that includes lithium ions
(Li*) at 2 keV, Li* ion implantation depth and lateral
distributions in panel A, depth versus ion current in panel B,
and total displacement in panel C for Monte Carlo simula-
tions for a 35-nm thick Si anode subjected to the 2 keV Li*;
FIG. 17 shows, for an ion beam that includes lithium ions
(Li*) at 10 keV, Li* ion implantation depth and lateral
distributions in panel A, depth versus ion current in panel B,
and total displacement in panel C for Monte Carlo simula-
tions for a 35-nm thick Si anode subjected to the 10 keV Li*;
FIG. 18 shows an exemplary lithium ion beam source; and
FIG. 19 shows in panel A an electron micrograph of a
silicon membrane with an inset that shows an ion-induced
secondary electron (iSE) image of annulus of ion beam
implanted lithium disposed in the silicon membrane after
lithium implantation; panel B shows normalized electron
energy-loss (EEL) spectra from site 1 and site 2 as marked
in an annular dark-field (ADF) scanning TEM (STEM)
image shown in the inset, wherein FEL spectra show a Li K
edge at 55 eV and the Si L, .-edge at 99 eV energy loss; and
panel C shows Li density map for lithium distributions with
Li* concentrations from 0 to 8-10"7 ion/em?.

DETAILED DESCRIPTION.

A detailed description of one or more embodiments is
presented herein by way of exemplification and not limita-
tion.

It has been discovered that a prelithiated lithium ion
battery and process for making the prelithiated lithium ion
battery provide doping and modifying battery components
with lithium ions (Li*) by ion implantation under vacuum,
ie, in a vacuum environment, without solvents or wet
chemistry processing for dry prelithiation of battery com-
ponents that increases an amount of active Li* in the
component. Active Li* refers to lithium ion available during
electrolyte electrochemical charge or discharge of the pre-
lithiated lithium ion battery. Without wishing to be bound by
theory, it is believed that the ion beam implanted lithium
present in components of the prelithiated lithium ion battery
is included as in an amorphized solid state. Advantageously,

articles and processes herein reduce an amount of side 5

reactions of electrode materials with liquid electrolyte to
increase capacity of the prelithiated lithium ion battery as
compared with conventional lithium ion batteries. Articles
and processes herein provide rechargeable cell systems such

as lithium-ion cells, lithium-metal cells, lithium-sulfur cells, s

lithium-air cells, lithium-carbon cells (e.g., a lithium-gra-
phene cell or a lithium-carbon nanotube cell), or a lithium-
ion supercapacitor, including symmetric and asymmetric
ultracapacitors, or hybrid energy storage or conversion sys
tems that use lithium ions. The process for making the
pfelithiated lithium ion battery includes dry, unsolvated,
lithium ions in a vacuum environment and overcomes tech-
nical problems with conventional wet or solvent-based elec-
trochemical making of batteries that include unwanted side
reactions of Li* that consume lithium. Beneficially, the
prelithiated lithium ion battery and processes described
provide direct dry lithiation using Li* implanted into elec-

20

3

&

&

4

trode material in vacuum. Various Li* sources, e.g., lithium
fast ion beam, provide a clean way to implant Li* that
overcomes complications from side reactions of lithium that
occur in conventional wet chemical or electrochemical pro-
cessing. Moreover, prelithiation of components of prelithi-
ated lithium ion battery overcomes problems of loss of
mobile Li* in electrode materials to improve performance of
prelithiated lithium ion battery compared with conventional
devices by providing relatively greater Coulombic efficiency
during initial cycle and subsequent cycle of operation of the
battery with greater rate capability, capacity retention,
energy, and power density.

Prelithiation and modification of battery components via
dose-controlled lithium ion implantation can enhance bat-
tery performance and can be applied to electrochemical
energy storage devices (e.g., batteries, supercapacitors,
hybrid systems, and the like) that include selected areas of
thin sheet or film electrodes, current collectors, or separa-
tors; particles (e.g., a solid powder) for a cathode or anode;
or solid electrolyte material that can be Li* source in the
prelithiated lithium ion battery.

In an embodiment, with reference to FIG. 1 and FIG. 2,
prelithiated lithium ion battery 200 includes: ion beam
implanted lithium 211; cathode 204; and anode 203 disposed

5 on cathode 204 and in electrical communication with cath-

ode 204, cathode 204 or anode 203 including ion beam
implanted lithium 211 such that: when cathode 204 includes
ion beam implanted lithium 211, ion beam implanted lithium
211 is present in cathode 204 prior to the SET formation; and
when anode 203 includes ion beam implanted lithium 211,
ion beam implanted lithium 211 is present in anode 203 prior
to the SEI formation.

In an embodiment, prelithiated lithium ion battery 200
further includes separator 206 interposed between anode 203
and cathode 204 and in electrical communication with anode
203 and cathode 204 such that lithium ions from ion beam
implanted lithium 211 communicate from anode 203 to
cathode 204 or from cathode 204 to anode 203 through
separator 206. According to an embodiment, separator 206
includes ion beam implanted lithium 211 prior to commu-
nication of lithium ions from any of anode 203 or cathode
204.

an embodiment, prelithiated lithium ion battery 200
includes cathode current collector 207 disposed on cathode
204 such that cathode 204 is interposed between anode 203
and cathodic current collector 207 with cathode current
collector 207 in electrical communication with cathode 204.
According to an embodiment, cathodic current collector 207
includes ion beam implanted lithium 211 prior to commu-
nication of lithium ions from cathode 204 and any other
portion of prelithiated lithium ion battery 200. Cathode
primer 209 can be disposed on cathode 204 such that
cathodic primer 209 is interposed between cathode current
collector 207 and cathode 204 with cathodic primer 209 in
electrical communication with cathode 204 and cathode
current collector 207. Further, cathode primer 209 can
include ion beam implanted lithium 211 prior to communi-
cation of lithium ions from cathode 204 and any other
portion of prelithiated lithium ion battery 200.

In an embodiment, prelithiated lithium ion battery 200
includes anode current collector 205 disposed on anode 203
such that anode 203 is interposed between cathode 204 and
anodic current collector 205 with anode current collector
205 in electrical communication with anode 203. According
to an embodiment, anode current collector 205 includes ion.
beam implanted lithium 211 prior to communication of
lithium ions from anode 203 and any other portion of



U.S. Patent Jan. 16, 2024 Sheet 16 of 19 US 11,876,211 B2

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Total Displacements
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Replacement Callisto:

Bas hacmmnmkes those.

FIG. 16


U.S. Patent Jan. 16, 2024 Sheet 8 of 19 US 11,876,211 B2

A) 210 |

203
208

vont
=
ite
iv
iD
a
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of eh 207

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FIG. 8


US 11,876,211 B2

17

The use of the terms “a” and “an” and “the” and similar
referents in the context of describing the invention (espe-
cially in the context of the following claims) are to be
construed to cover both the singular and the plural, unless
otherwise indicated herein or clearly contradicted by con-
text. “Or” means “and/or.” It should further be noted that the
terms “first,” “second,” “primary,” “secondary,” and the like
herein do not denote any order, quantity, or importance, but
rather are used to distinguish one element from another. The
modifier “about” used in connection with a quantity is
inclusive of the stated value and has the meaning dictated by
the context (e.g., it includes the degree of error associated
with measurement of the particular quantity). The conjune-
tion “or” is used to link objects of a list or alternatives and
is not disjunctive; rather the elements can be used separately
‘or can be combined together under appropriate circum-
stances.

What is claimed is:

1. A process for making a prelithiated lithium ion battery,
the process comprising:

subjecting the first battery member to a lithium ion beam

comprising lithium ions;

implanting ion beam implanted lithium from the lithium

ion beam in the first battery member to prelithiated the
first battery member;

disposing a second battery member on a first battery

member;

disposing a third battery member on the second battery

member so that the second battery member is inter-
posed between the first battery member and the third
battery member to form a prelithiated battery compos-
ite; and

annealing the prelithiated battery composite to form the

prelithiated lithium ion battery such that the prelithiated
lithium ion battery has an absence of a solid electrolyte
interface composition in a portion of the first battery
member subjected to implanting the ion beam
implanted lithium from the lithium ion beam.

2. The process of claim 1, further comprising, prior to
disposing the second battery member on the first battery
member:

subjecting the second battery member to the lithium ion

beam; and

implanting the ion beam implanted lithium from the

lithium ion beam in the second battery member to
prelithiated the second battery member.

3. The process of claim 2, further comprising, prior to
disposing the third battery member on the second battery
member:

subjecting the third battery member to the lithium ion

beam; and

implanting the ion beam implanted lithium from the

lithium ion beam in the third battery member to pre-
lithiated the second battery member.

4. The process of claim 1, further comprising, prior to
disposing the third battery member on the second battery
memb«

subjecting the third battery member to the lithium ion

beam; and

implanting the ion beam implanted lithium from the

lithium ion beam in the third battery member to pre-
lithiated the second battery member.

5. The process of claim 1, wherein:

the first battery member comprises a cathodic member or

an anodic member;

the second battery member comprises an intermediate

member;

0

5

20

0

38

&

0

45

50

35

at

0

65

18

when the first battery member is the cathodic member, the
third battery member comprises the anodic member;
and

when the first battery member is the anodic member, the

third battery member comprises the cathodic member.

6. The process of claim 5, wherein:

the first battery member comprises the anode member;

and

the third battery member comprises the cathode member.

7. A process for making a prelithiated lithium ion battery,
the process comprising:

disposing electrode particles in a vacuum environment;

subjecting the electrode particles to a lithium ion beam

comprising ion beam implanted lithium;
implanting ion beam implanted lithium from the lithium
ion beam in the electrode particles to prelithiated the
electrode particles with ion beam implanted lithium;

combining, after implanting ion beam implanted lithium
in the electrode particles, the electrode particles with a
conductive additive and a binder to form an electrode
composition;

disposing, as a first electrode, the electrode composition

on a first current collector to form a first electrode
member such that the first electrode comprises the ion
beam implanted lithium that is present in absence of
solid electrolyte interface composition in the first elec-
trode;

annealing the first electrode member; and

disposing the first electrode member on a second elec-

trode member to make the prelithiated lithium ion
battery.
8. The process of claim 7 for making the prelithiated
lithium ion battery, the process further comprising, prior to
disposing the first electrode on the first current collector:
subjecting the first current collector to the lithium ion
beam comprising ion beam implanted lithium;

implanting ion beam implanted lithium from the lithium
ion beam in the first current collector to prelithiated the
first current collector with ion beam implanted lithium,
wherein the first current collector comprises the ion
beam implanted lithium that is present in absence of
solid electrolyte interface composition in the first cur-
rent collector; and

annealing the first current collector.

9. The process of claim 7 for making the prelithiated
lithium ion battery, the process further comprising, prior to
disposing the first electrode member on the second electrode
member:

disposing, as a second electrode, the electrode composi-

tion on a second current collector to form the second
electrode member such that the second electrode com-
prises the ion beam implanted lithium that is present in
absence of solid electrolyte interface composition in the
second electrode; and

annealing the second electrode member.

10. The process of claim 9 for making the prelithiated
lithium ion battery, the process further comprising, prior to
disposing the second electrode on the second current col-
lector:

subjecting the second current collector to the lithium ion

beam comprising ion beam implanted lithium;
implanting ion beam implanted lithium from the lithium
ion beam in the second current collector to prelithiated
the second current collector with ion beam implanted
lithium, wherein the second current collector comprises
the ion beam implanted lithium that is present in



U.S. Patent Jan. 16, 2024 Sheet 5 of 19 US 11,876,211 B2

204 Nozzle
Cathode .

XK current
collector

207

FIG. 5


U.S. Patent Jan. 16, 2024 Sheet 4 of 19 US 11,876,211 B2

FIG. 4


U.S. Patent Jan. 16, 2024 Sheet 17 of 19 US 11,876,211 B2

S

ee TON RANGES

Kon Runge > 3868 Shemeaeas © 438EE
= Ras

Seraggis = BEA Rurtosis

z
.

{ATOMS /omS) f§ (ATOMS / om)

Total Displacements

Total Displacements « 44 / Ion

Total Vavancivs « 407 fon

Replacement Collisions #8 slong
Blas &

Pt

g g

FIG. 17


U.S. Patent Jan. 16, 2024 Sheet 7 of 19 US 11,876,211 B2

(Cy

(A) 215 (D) 213 hoz
209

204 2 0 PP gL any

> ite
iS s
N50 [Go

i
Ir

(E) 200

ee 204 Oo Qt~211
(By 206 ee 206

208

FIG. 7


US 11,876,211 B2

7

transport and improve the performance of the battery during
electrochemical charge-discharge cycling under optimized
processing conditions; annealing the first electrode member;
and disposing the first electrode member on a second
electrode member to make the prelithiated lithium ion
battery.

In an embodiment, a process for making a prelithiated
lithium ion battery, the process comprising: forming a first
current collector; forming a cathode on the first current
collector; forming an electrolyte on the cathode; forming an
anode on the cathode; subjecting the anode to a lithium ion
beam comprising lithium ions; implanting lithium ions from
the lithium ion beam in the anode to prelithiate the anode
with ion beam implanted lithium such that the anode com-
prises the ion beam implanted lithium that creates internal
sub-surface reservoirs of mobile lithium ions in an excess of
stoichiometry, which compensate for lithium losses due to
the formation of the SEI, stabilizes the SEI and induces
controlled solid-state amorphization and modification of the

anode by creating structural defects, dangling bonds, diffu- 2

sion channels, and pathways that enable to facilitate ion
transport and improve the performance of the battery during
electrochemical charge-discharge cycling under optimized
processing conditions; annealing the anode after implanting
lithium ions in the anode;
on the anode; and annealing the second current collector to
form the prelithiated lithium ion battery.

In an embodiment, a process for making a prelithiated
lithium ion battery, the process comprising: forming a first
current collector; forming a second current collector; form-
ing a cathode on the first current collector, the cathode
comprising an interdigitated structure that is in electrical
communication with the first current collector; forming an
anode on the second current collector, the anode comprising
a second interdigitated structure that is in electrical com-
munication with the second current collector; subjecting the
anode to a lithium ion beam comprising lithium ions;
implanting lithium ions from the lithium ion beam in the
anode to prelithiate the anode with ion beam implanted
lithium such that the anode comprises the ion beam
implanted lithium that creates internal sub-surface reservoirs
of mobile lithium ions in an excess of stoichiometry, which
compensate for lithium losses due to the formation of the
SEI, stabilizes the SEI and induces controlled solid-state
amorphization and modification of the anode by creating
structural defects, dangling bonds, diffusion channels, and
pathways that enable to facilitate ion transport and improve
the performance of the battery during electrochemical
charge-discharge cycling under optimized processing con-
ditions;
ing lithium ions in the anode; and disposing an electrolyte on
the on the cathode and the anode so that lithium ions are
communicated through the electrolyte from the anode to the
cathode or from the cathode to the anode to make the
prelithiated lithium ion battery.

‘Components of prelithiated lithium ion battery 200 can be
made from and include various materials. Anode 203 (also
referred to as a negative electrode) can receive or provide
Lit from ion beam implanted lithium 211. Anode 203
provides mechanical structure for disposition of other ele-
ments of prelithiated lithium ion battery 200 thereon. Anode
203 can include a carbon (e.g., carbon, mesocarbon, soft
carbon, hard carbon, carbon black, activated carbon, graph-
ite, pyrolytic graphite, exfoliated graphite, carbon fiber,
carbon nanofiber, carbon nanotube, graphene flake, gra-
phene oxide, nitrogen doped graphene, graphene fluoride,
graphene fiber, graphene whisker, and coke); silicon, ger-

forming a second current collector 2

innealing the anode and the cathode after implant- 5

&

&

s

8

manium, tin, lead, antimony, bismuth, zinc, aluminum, cad-
mium, or stoichiometric or non-stoichiometric alloys thereof
with other elements; oxide, carbide, nitride, sulfide, phos-
phide, selenide, or telluride of silicon, germanium, tin, lead,
antimony, bismuth, zinc, aluminum, iron, titanium, manga-
nese, cobalt, molybdenum, tungsten, cadmium, or combi-
nation thereof including a composite thereof, or a combi-
nation including at least one of the foregoing. A thickness of
anode 203 can be from 1 nm to 1 cm, specifically from 1 jum
to 10 mm, and more specifically from 10 jum to 100 pm. A
density of ion beam implanted lithium 211 in anode 203 can
be from 0 atoms/cm? to 10'° atoms/cm’, specifically from
100 atoms/cm to 10° atoms/em*, and more specifically from
1000 atoms/cm* to 10° atoms/cm’. In an embodiment, anode
203 is silicon.

Cathode 204 (also referred to as a positive electrode) can
receive or provide Li+ from ion beam implanted lithium 211.
Cathode 204 can be a lithiated or non-lithiated transition
metal oxide (e.g., lithium cobalt oxide, lithium manganese
dioxide, or lithium manganese composite oxide, lithium
nickel oxide, lithium vanadium oxide, or lithium iron phos-
phate; cobalt dioxide, vanadium oxide), transition metal
dichalcogenide such as titanium disulfate, molybdenum
disulfate, tungsten disulfate, molybdenum diselenide, tung-
sten diselenide, or a combination thereof. A thickness of
cathode 204 can be from 1 nm to 1 cm, specifically from 1
jum to 10 mm, and more specifically from 10 um to 100 um.
A density of ion beam implanted lithium 211 in cathode 204
can be from 0 atoms/cm* to 10*° atoms/cm’, specifically
from 100 atoms/cm’ to 10* atoms/cm’, and more specifically
froth 1000 atoms/cm* to 10° atoms/cm’. In an embodiment,
cathode 204 is silicon.

Anode current collector 205 is compatible with the anode
and electrolyte without causing corrosion and can receive or
provide electrons as electrical current, voltage, or charge
accumulation with uniform current distribution and low
contact resistance to minimize anode polarization during
cycling. Anode current collector 205 can include a copper,
nickel, and aluminum metals and alloys, graphite and other
conductive carbons, conductive ceramic, and polymers. A
thickness of anode current collector 205 can be from 1 nm
to 1 om, specifically from 1 jm to 10 mm, and more
specifically from 10 jum to 100 jm. A density of ion beam
implanted lithium 211 in anode current collector 205 can be
from 0 atoms/cm? to 10'° atoms/em:, specifically from 100
atoms/cm* to 10° atoms/em*, and more specifically from
1000 atoms/cm* to 10° atoms/cm’.

Separator 206 electrically and spatially separates elec-
trodes (203, 204) and can receive or provide Li+ from ion
beam implanted lithium 211, facilitating diffusion of Li+
between electrodes (e.g., 203, 204), and. Separator 206 is
formed from a porous material soaked with electrolyte and
communicates with the electrodes (203, 204). Separator 206
can be formed from polymers such as polyethylene, poly-
propylene, or polyvinylidene fluoride, ceramic or glass. A
thickness of separator 206 can be from 1 nm to | cm,
specifically from 1 jm to 10 mm, and more specifically from
10 jum to 100 um. A density of ion beam implanted lithium
211 in separator 206 can be from 0 atoms/cm’ to 10'°
atoms/cm’, specifically from 100 atoms/cm? to 10* atoms/
cm®, and more specifically from 1000 atoms/cm? to 10°
atoms/cm*.

Cathodic current collector 207 can receive or provide
electrons as electrical current, voltage, or charge accumula-
tion. Anodic current collector 205 can include copper, alu-
minum, nickel metals and alloys, graphite and conductive
carbons, conductive ceramic, and polymers. A thickness of



United States Patent

US011876211B2

(12) (0) Patent No.: US 11,876,211 B2
Oleshko et al. (45) Date of Patent: Jan. 16, 2024
(54) PRELITHIATED LITHIUM ION BATTERY (52) US. Ch
AND MAKING A PRELITHIATED LITHIUM cp HOIM 4/134 (2013.01); HOIM 4/0423
ION BATTERY (2013.01); HOIM 4/1395 (2013.01):
(Continued)
(71) Applicant: Government of the United States of (58) Field of Classification Search
America, as represented by the CPC sss YO2E 60/10; YO2P 70/50; YO2T 10/70:
Secretary of Commerce, Gaithersburg, HOIM 4/134; HOIM 4/1395; HOIM
MD (US) 4/661; HOIM 4/666
See application file for complete search history.
(72) Inventors: Vladimir Pavlovich Oleshko,
Gaithersburg, MD (US); Christopher (56) References Cited
Lloyd Soles, Boyds, MD (US); Jabez
Jenkins McClelland, Bethesda, MD U.S. PATENT DOCUMENTS
(US) 8,530,853 B2" 9/2013 Steele .. .. HOLI 27/022
250/423 P
(73) Assignee: GOVERNMENT OF THE UNITED 9,385,397 B2 7/2016 Zhamu et al
STATES OF AMERICA, AS (Continued)
REPRESENTED BY THE
SECRETARY OF COMMERCE, OTHER PUBLICATIONS
Gaithersburg, MD (US)
Xu, K., et al., “Lil-solvation/desolvation dictates interphasial pro-
(*) Notice: Subject to any disclaimer, the term of this cesses on graphitic anode in Li ion cells”, Journal of Materials
patent is extended or adjusted under 35 Research, 2012, p. 2327-2341, vol. 27 No.18.
USC. 154(b) by 412 days. (Continued)
(21) Appl. No.: 17/018,898 Primary Examiner — Amanda C. Walke
(74) Attorney, Agent, or Firm — Office of Chief Counsel
(22) Filed: Sep. 11, 2020 for National Institute of Standards and Technology
(65) Prior Publication Data 67) ABSTRACT
A prelithiated lithium ion battery includes: ion beam
US 2021/0075001 Al = Mar. 11, 2021 implanted lithium; a cathode; and an anode disposed on the
cathode and an electrolyte in electrical communication with
the cathode and the anode, the cathode or the anode includ-
Related U.S. Application Data ing the ion beam implanted lithium such that: when the
(60) Provisional application No. 62/898,886, filed on Sep. cathode includes the ion beam implanted lithium, the ion
11, 2019. beam implanted lithium is present in an absence of solid
° electrolyte interface composition in the cathode; and when
(51) Int.Ch the anode includes the ion beam implanted lithium, the ion
‘HOIM 4/134 (2010.01) beam implanted lithium is present in an absence of solid
HOIM 10/0525 (2010.01) electrolyte interface composition in the anode.
(Continued) 16 Claims, 19 Drawing Sheets
200

pV 214
> 214

7,21
21h



U.S. Patent Jan. 16, 2024 Sheet 10 of 19 US 11,876,211 B2

©) 233

(A) 207
215 202
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210
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205 © 0° Code 214 241

FIG. 10


U.S. Patent Jan. 16, 2024 Sheet 9 of 19 US 11,876,211 B2

(A) 215
v
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209
203 204
208
208
v
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aos Fo FF oy

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FIG. 9


US 11,876,211 B2

19

absence of solid electrolyte interface composition in the
second current collector; and

annealing the first current collector.

11. A process for making a prelithiated lithium ion battery,
the process comprising:

forming a first current collector;

forming a cathode on the first current collector;

forming an electrolyte on the cathode;

forming an anode on the cathode;

subjecting the anode to a lithium ion beam comp:

beam implanted lithium;

implanting ion beam implanted lithium from the lithium

ion beam in the anode to prelithiated the anode with ion
beam implanted lithium such that the anode comprises
the ion beam implanted lithium that is present in
absence of solid electrolyte interface composition in the
anode;

annealing the anode after implanting ion beam implanted

lithium in the anode;

forming a second current collector on the anode; and

annealing the second current collector to form the pre-

lithiated lithium ion battery.
12. The process of claim 11 for making the prelithiated
lithium ion battery, the process further comprising, prior to
forming the cathode on the first current collector
subjecting the first current collector to the lithium ion
beam comprising ion beam implanted lithium;

implanting ion beam implanted lithium from the lithium
ion beam in the first current collector to prelithiated the
first current collector with ion beam implanted lithium;
and

annealing the first current collector after implanting the

ion beam implanted lithium in the first current collec-
tor.
13. The process of claim 11 for making the prelithiated
lithium ion battery, the process further comprising, prior to
annealing the second current collector:
subjecting the second current collector to the lithium ion
beam comprising ion beam implanted lithium; and

implanting ion beam implanted lithium from the lithium
ion beam in the second current collector to prelithiated
the second current collector with ion beam implanted
lithium.

14. A process for making a prelithiated lithium ion battery,
the process comprising:

forming a first current collector;

sing ion

20

0

4

0

20

forming a second current collector;
forming a cathode on the first current collector, the
cathode comprising an interdigitated structure that is in
electrical communication with the first current collec-
tor;
forming an anode on the second current collector, the
anode comprising a second interdigitated structure that
is in electrical communication with the second current
collector;

subjecting the anode to a lithium ion beam comprising ion

beam implanted lithium;

implanting ion beam implanted lithium from the lithium

ion beam in the anode to prelithiated the anode with ion
beam implanted lithium such that the anode comprises
the ion beam implanted lithium that is present in
absence of solid electrolyte interface composition in the
anode;

annealing the anode and the cathode after implanting ion

beam implanted lithium in the anode; and
disposing an electrolyte on the on the cathode and the
anode so that lithium ions are communicated through
the electrolyte from the anode to the cathode or from
the cathode to the anode to make the prelithiated
lithium ion battery.
15. The process of claim 14 for making the prelithiated
lithium ion battery, the process further comprising, prior to
forming the cathode on the first current collector:
subjecting the first current collector to the lithium ion
beam comprising ion beam implanted lithium;

implanting ion beam implanted lithium from the lithium
ion beam in the first current collector to prelithiated the
first current collector with ion beam implanted lithium;
and

annealing the first current collector after implanting the

ion beam implanted lithium in the first current collec-
tor.
16. The process of claim 11 for making the prelithiated
lithium ion battery, the process further comprising, prior to
forming the anode on the second current collector:
subjecting the second current collector to the lithium ion
beam comprising ion beam implanted lithium; and

implanting ion beam implanted lithium from the lithium
ion beam in the second current collector to prelithiated
the second current collector with ion beam implanted
lithium.


U.S. Patent Jan. 16, 2024 Sheet 6 of 19 US 11,876,211 B2

(A) 210 - ©)
203 207
208 209
205 204

BUS HPT SeoSL yy ©) 203
208
205 9 0 9 Sodan
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206
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FIG. 6


US 11,876,211 B2

1
PRELITHIATED LITHIUM ION BATTERY
AND MAKING A PRELITHIATED LITHIUM
TON BAI RY

CROSS REFERENCE TO RELATED,
APPLICATION

This application claims the benefit of U.S. Provisional
Patent Application Ser. No. 62/898,886 filed Sep. 11, 2019,
the disclosure of which is incorporated herein by reference
in its entirety.

STATEMENT REGARDING FEDERALLY,
SPONSORED RESEARCH

‘This invention was made with United States Government
support from the National Institute of Standards and Tech-
nology (NIST), an agency of the United States Department
of Commerce. The Government has certain rights in the
invention. Licensing inquiries may be directed to the Tech-
nology Partnerships Office, NIST, Gaithersburg, MD,
20899; voice (301) 301-975-2573; email tpo@nist. gov; ref-
erence NIST Docket Number 18-030USI.

BRIEF DESCRIPTION

Disclosed is a prelithiated lithium ion battery comprising:
ion beam implanted lithium; a cathode; and an anode
disposed on the cathode and in electrical communication
with the cathode, the cathode or the anode comprising the
ion beam implanted lithium such that: when the cathode
comprises the ion beam implanted lithium, the ion beam
implanted lithium is present in an absence of solid electro-
lyte interface composition in the cathode; and when the
anode comprises the ion beam implanted lithium, the ion
beam implanted lithium is present in an absence of solid
electrolyte interface composition in the anode.

Disclosed is a process for making a prelithiated lithium
ion battery, the process comprising: disposing a first battery
member in a vacuum environment; subjecting the first
battery member to a lithium ion beam comprising lithium
ions; implanting lithium ions from the lithium ion beam in
the first battery member to prelithiate the first battery
member; disposing a second battery member on a first
battery member; disposing a third battery member on the
second battery member so that the second battery member is
interposed between the first battery member and the third
battery member to form a prelithiated battery composite; and
annealing the prelithiated battery composite to form the

prelithiated lithium ion battery such that the prelithiated s

lithium ion battery has an absence of a solid electrolyte
interface composition in a portion of the first battery mem-
ber subjected to implanting the lithium ions from the lithium
ion beam.

Disclosed is a process for making a prelithiated lithium

ion battery, the process compri
particles in a vacuum environme!
particles to a lithium ion beam comprising lithium ions;
implanting lithium ions from the lithium ion beam in the
electrode particles to prelithiate the electrode particles with
ion beam implanted lithium; combining, after implanting
lithium ions in the electrode particles, the electrode particles
with a conductive additive and a binder to form an electrode
composition; disposing, as a first electrode, the electrode
composition on a first current collector to form a first
electrode member such that the first electrode comprises the
ion beam implanted lithium that is present in absence of

20

2

solid electrolyte interface composition is present in absence
of solid electrolyte interface composition in the first elec-
trode; annealing the first electrode member; and disposing
the first electrode member on a second electrode member to
make the prelithiated lithium ion battery.

Disclosed is a process for making a prelithiated lithium
ion battery, the process comprising: forming a first current
collector; forming a cathode on the first current collector;
forming an electrolyte on the cathode; forming an anode on
the cathode; subjecting the anode to a lithium ion beam
comprising lithium ions; implanting lithium ions from the
lithium ion beam in the anode to prelithiate the anode with
ion beam implanted lithium such that the anode comprises
the ion beam implanted lithium that is present in absence of
solid electrolyte interface composit resent in
absence of solid electrolyte interface composition in the
anode; annealing the anode after implanting lithium ions in
the anode; forming a second current collector on the anode;
and annealing the second current collector to form the
prelithiated lithium ion battery.

Disclosed is a process for making a prelithiated lithium
ion battery, the process comprising: forming a first current
collector; forming a second current collector; forming a
cathode on the first current collector, the cathode comprising

San interdigitated structure that is in electrical communication

with the first current collector; forming an anode on the
second current collector, the anode comprising a second
interdigitated structure that is in electrical communication
with the second current collector; subjecting the anode to a
lithium ion beam comprising lithium ions; implanting
lithium ions from the lithium ion beam in the anode to
prelithiate the anode with ion beam implanted lithium such
that the anode comprises the ion beam implanted lithium
that is present in absence of solid electrolyte interface
composition in is present in absence of solid electrolyte
interface composition in the anode; annealing the anode and
the cathode after implanting lithium ions in the anode; and
disposing an electrolyte on the on the cathode and the anode
so that lithium ions are communicated through the electro-
lyte from the anode to the cathode or from the cathode to the
anode to make the prelithiated lithium ion battery.

BRIEF DESCRIPTION OF THE DRAWINGS

‘he following description should not be considered lim-
iting in any way. With reference to the accompanying
drawings, like elements are numbered alike.

FIG. 1 shows a prelithiated lithium ion battery;

FIG. 2 shows a prelithiated lithium ion battery;

FIG. 3 shows a prelithiated lithium ion battery;

FIG. 4 shows a prelithiated lithium ion battery;

FIG. 5 shows a prelithiated lithium ion battery;

FIG. 6 shows steps in making a prelithiated lithium ion
battery;

FIG. 7 shows steps in making a prelithiated lithium ion
battery;

FIG. 8 shows steps in making a prelithiated lithium ion
battery;

FIG. 9 shows steps in making a prelithiated lithium ion
battery;

FIG. 10 shows steps in making a prelithiated lithium ion
battery;

FIG. 11 shows steps in making a prelithiated lithium ion
battery;

FIG. 12 shows a plurality of different paths of an ion beam
‘on a component, ¢.g., a cathodic current collector, of a
prelithiated lithium ion battery for a strip path in panel A, a


US 11,876,211 B2

13

204 on the first current collector; forming electrolyte 223 on
cathode 204; forming anode 203 on cathode 204; subjecting
anode 203 to lithium ion beam 210 including ion beam
implanted lithium 211; implanting ion beam implanted
lithium 211 from lithium ion beam 210 in anode 203 to
prelithiate anode 203 with ion beam implanted lithium such
that anode 203 includes ion beam implanted lithium that is
present in absence of solid electrolyte interface composition
in anode 203; annealing anode 203 after implanting ion
beam implanted lithium 211 in anode 203; forming a second
current collector on anode 203; and annealing the second
current collector to form prelithiated lithium ion battery 200.

The process further can include, prior to forming cathode
204 on the first current collector: subjecting the first current
collector to lithium ion beam 210 including ion beam
implanted lithium 211; implanting ion beam implanted
lithium 211 from lithium ion beam 210 in the first current
collector to prelithiate the first current collector with ion

beam implanted lithium; and annealing the first current 2

collector after implanting ion beam implanted lithium 211 in
the first current collector.

‘The process further can include, prior to annealing the
second current collector: subjecting the second current col-
lector to lithium ion beam 210 including ion beam implanted
lithium 211; and implanting ion beam implanted lithium 211
from lithium ion beam 210 in the second current collector to
prelithiate the second current collector with ion beam
implanted lithium.

In an embodiment, with reference to FIG. 5 and FIG. 15,
a process for making prelithiated lithium ion battery 200
includes: forming a first current collector; forming a second
current collector; forming cathode 204 on the first current
collector, cathode 204 including an interdigitated structure
that is in electrical communication with the first current
collector; forming anode 203 on the second current collec-
tor, anode 203 including a second interdigitated structure
that is in electrical communication with the second current
col lector; subjecting anode 203 to a lithium ion beam 210
including ion beam implanted lithium 211; implanting ion
beam implanted lithium 211 from lithium ion beam 210 in
anode 203 to prelithiate anode 203 with ion beam implanted
lithium such that anode 203 includes ion beam implanted
lithium that is present in absence of solid electrolyte inter-
face composition in anode 203; annealing anode 203 and
cathode 204 after implanting ion beam implanted lithium
211 in anode 203; and disposing electrolyte 223 on anode
203 and cathode 204 so that lithium ions are communicated
through electrolyte 223 from anode 203 to cathode 204 or

from cathode 204 to anode 203 to make prelithiated lithium 5

ion battery 200.

‘The process further can include, prior to forming cathode
204 on the first current collector: subjecting the first current
collector to lithium ion beam 210 including ion beam

implanted lithium 211; implanting ion beam implanted s

lithium 211 from lithium ion beam 210 in the first current
collector to prelithiate the first current collector with ion
beam implanted lithium; and annealing the first current
collector after implanting ion beam implanted lithium 211 in
the first current collector.

The process further can include, prior to forming anode on
the second current collector: subjecting the second current
collector to lithium ion beam 210 including ion beam
implanted lithium 211; and implanting ion beam implanted
lithium 211 from lithium ion beam 210 in the second current
collector to prelithiate the second current collector with ion
beam implanted lithium.

&

&

at

14

It will be appreciated that in making prelithiated lithium
ion battery 200 elements thereof are arranged with compo-
nents to be in communication so that lithium ions from ion
beam implanted lithium 211 separator 206 propagates from
anode 203 with production of cathodic current collector 207
and solid electrolyte interface composition reception of
cathodic member 213 by prelithiated battery composite 218
and arranging optical components to be in optical commu-
nication and electrical components to communicate electri-
cal signals amongst the various electrical components
Controlled dose implantation of Li* for prelithiation of
electrodes, materials for electrodes, and other components
(eg., separators, solid electrolytes, current collectors) for
lithium-based electrochemical energy storage devices
includes prelithiated lithium ion battery 200. FIG. 6 shows
implanting Li* into different components to make prelithi-
ated lithium ion battery 200. An exemplary source of Li*
from lithium ion beam 210 is an ultra-cold focused Li*ion
beam device that locally implants Li* into a component for
prelithiated lithium ion battery 200. Directly injecting dry
Li* in a vacuum environment and in an absence of a liquid
electrolyte for transport of Li* provides reduction of initial
irreversible capacity losses due to the formation of solid
electrolyte interface composition that can occur as a layer on

5 an electrode that would affect Li* diffusion from electrolyte

into electrodes. Solid electrolyte interface composition can
form from electrochemical reactions of Li* in solution,
liquid electrolyte, and an electrified interface of an electrode.
Processes for making prelithiated lithium ion battery 200
avoid formation of solid electrolyte interface composition
and provide direct prelithiation by dry, in-vacuo e.g., from a
LiF IB, that is clean without side reactions from wet chemi-
cal or electrochemical processing. Making prelithiated
lithium ion battery 200 can include various positive elec-
trode material, negative electrode material, or electrochemi-
cal energy storage devices such as rechargeable powder-
based lithium-ion or lithium-metal cells, lithium-sulfur
(Li—S) cells, lithium-air (Li-air(O,) batteries (FIG. 3), 3D
structured and all solid-state Li-based batteries (FIG. 4, FIG.
5), supercapacitors symmetric, asymmetric, hybrid, or
lithium-ion supercapacitors, hybrid energy storage or con-
version systems, or their components as exemplary formats
for cells.

It should be appreciated that in making prelithiated
lithium ion battery 200 prelithiation can be conducted on
sheets, films, or powders of composite intercalation and
conversion positive electrodes (FIG. 7), negative electrodes
(FIG. 8), separators, solid electrolytes (FIG. 9), primer
layers, or current collectors (FIG. 10).

Prelithiated lithium ion battery 200 and process herein
overcome conventional practices for introducing lithium
ions into the electrode materials. Conventional methods
include chemical or electrochemical steps that use reactive
Li-containing reagents such as sacrificial additives, donors,
mixing with stabilized lithium metal powder (SLMP),
organic solvents, or lithium salts in liquid electrolytes that
wet metallic lithium foils to introduce lithium species into
the material under an electrochemical potential. Under these
conditions, lithium-consuming side reactions occur between
components and create an SEI layer on the electrode. The
SEI layer decreases battery capacity by increasing the
impedance of a system and is a physical and chemical barrier
that Li* must propagate through to reach active electrode
material.

Making the prelithiated lithium ion battery 200 implants
Li* directly in material without wet chemical or electro-
chemical prelithiation with liquid electrolytes or metallic



U.S. Patent Jan. 16, 2024 Sheet 2 of 19 US 11,876,211 B2

bo
I>

FIG. 2


U.S. Patent Jan. 16, 2024 Sheet 13 of 19 US 11,876,211 B2

Powders for high capacity anodes (Si, graphite) |
=

Prelithiation & modification by controlied Li” implantation

aw

Mixing with conductive additive & binder

z=

| Coating of the raixture to current collector

Rw Current collector
Winding, drying & annealing of composite
electrades

Controlled L° implantation for creation of
Rea internal Li reservoirs

Cutting, calendaring & slitting af electrades ta
desired length, thickness and widtty

atid

Current collector tab welding & isolation ce

x

Enhanced performance high capacity anode |

=

Cell aesembling

Annealing

FIG. 13


U.S. Patent Jan. 16, 2024 Sheet 15 of 19 US 11,876,211 B2

[ Fabrication of isolated substrate or scaffold structure |

=.
| Patterning of current collector ] b

Contatiad LP implantation for creation of
internal Li reservoirs followed by annealing

Printing of a 3D high capacity interdigitated cathode
with a cathode ink

Printing of a 3D high capacity interdigitated anode
with an anode ink

Ewen

[ Prelithiation & modification of anodes by controlled Li" implantation |

bea

[[ Annealing (sintering) of electrodes}
a

[injection of a fiquid (gel) electratyte |

=

Packaging & isolation

Additive manufacturing (30 printing} of microbatteries

Making interdigitated 3D Li ion microbattery with pre-lithiated enhanced
high capacity anode and liquid electrolyte

FIG. 15


U.S. Patent Jan. 16, 2024 Sheet 1 of 19 US 11,876,211 B2

Ine
iS

213

cet 2EL

ro 214
ods 211

- Ais
"ets 211

FIG. J


US 11,876,211 B2

9

cathodic current collector 207 can be from 1 nm to 1 cm,
specifically from 1 jum to 10 mm, and more specifically from
10 um to 100 pm. A density of ion beam implanted lithium
211 in cathode current collector 207 can be from 0 atoms/
cm} to 10'° atoms/cm*, specifically from 100 atoms/cm* to
10° atoms/cm?, and more specifically from 1000 atoms/cm?
to 10° atoms/em*.

Primer layers for enhancing adhesive strength between
the current collector and the electrode and maintaining
stability of the battery under operating conditions without
increasing internal resistance. Primer layers
primer 208, cathode primer 209) independently
conductive carbons and polymeric binders. A thickness of
primer layers (e.g., anode primer 208, cathode primer 209)
independently can be from 1 nm to 1 cm, specifically from
1 um to 10 mm, and more specifically from 10 jum to 100
ym. A density of ion beam implanted lithium 211 in primers
(e.g., anode primer 208, cathode primer 209) independently
can be from 0 atoms/cm? to 10! atoms/em®, specifically
from 100 atoms/em® to 10° atoms/em?, and more specifically
from 1000 atoms/cm* to 10° atoms/em*

Lithium ion beam 210 can provide lithium ions. Lithium
ion beam 210 can include lithium ions in isolation or in
combination with a diluent gas such as argon, helium, and

the like. Lithium ion beam 210 has an absence of material 2

that can form solid electrolyte interface composition in a
presence of lithium implanted from Li* in lithium ion beam
210. An exemplary source for making lithium ion beam 210
is a field emission source, fast ion bombardment source,
flood source, and the like, e.g., MOTIS source shown in FIG.
18. A diameter of lithium ion beam 210 can be from 1 nm
to 1 cm, specifically from 1 ym to 10 mm, and more
specifically from 10 um to 100 um. A cross-sectional shape
of lithium ion beam 210 can be formed or manipulated by
ion optics and can be scanned across a surface in a raster or
other pattern. It is contemplated that a length or width of
lithium ion beam 210 can be from 1 nm to I cm, specifically
from 1 um to 10 mm, and more specifically from 10 jum to
100 tm. A flux of lithium ions in lithium ion beam 210 can
be from 0 ions/em’s to 10° ions/cm?s, specifically from 1
ion/em’s to 10° ions/em?s, and more specifically’ from 10
jons/em?s to 1000 ions/em?s. A number density of lithium
ions lithium ion beam 210 can be from 0 ions/em* to 10°°
ions/em®, specifically from 100 ions/cm* to 10° ions/em>,
and more specifically from 1000 ions/em* to 10° ions/em?.
Further, lithium ion beam 210 can have an energy from 1 eV
to 1 MeV, specifically from 100 eV to 100 keV, and more
specifically from 1000 eV to 10 keV. In an embodiment,
lithium ion beam 210 is configured to have dimension and

shape matching the substrate size and shape such that entire s

surface is implanted at a depth of 0.1 um to 10 um without
changing any parameters. In another embodiment, lithium
ion beam 210 is in the form of a narrow beam that is scanned
across the substrate surface to implant ions at a depth of 0.1
gum to 10 ym.

Jon beam implanted lithium 211 provide lithium ions as
electrical current, voltage, or charge accumulation in pre-
lithiated lithium ion battery 200. Ion beam implanted lithium
211 can include lithium atoms as an atomic species in
absence of lithium-containing molecules or lithium ions as
ionic species Li* in absence of lithium-containing complex
ions. A thickness, e.g. a depth of penetration ina component
(e.g., anode 203, cathode 204, and the like) of prelithiated
lithium ion battery 200 due to implantation of lithium ions
from lithium ion beam 210, of ion beam implanted lithium
211 can be from I nm to 1 cm, specifically from 1 pm to 10
mm, and more specifically from 10 um to 100 um. A density

20

&

&

s

10
of ion beam implanted lithium 211 in a component (e.g.,
anode 203, cathode 204, and the like) of prelithiated lithium,
ion battery 200 can be from 0 atoms/em* to 10!° atoms/em?,
specifically from 100 atoms/cm: to 10 atoms/em*, and more
specifically from 1000 atoms/cm? to 10° atoms/em?.

Prelithiated lithium ion battery 200 overcomes issues of
conventional lithium ion batteries that include solid electro-
lyte interface composition. In operating a conventional
lithium ion battery, solid electrolyte interface composition
accordingly incorporates lithium and decreases an amount of
lithium that available as Li* for communication as electrical
charge in the conventional lithium ion battery. Since lithium.
ion beam 210 implants ion beam implanted lithium 211
directly in components of (e.g., anode 203, cathode 204, and
the like) of prelithiated lithium ion battery 200, it should be
appreciated that lithium in ion beam implanted lithium 211
does not form solid electrolyte interface composition and is
freely available from ion beam implanted lithium 211 as Li+
to communicate as electrical charge in prelithiated lithium
ion battery 200.

In making prelithiated lithium ion battery 200, a vacuum
environment 217 is used during implantation of lithium ions
as ion beam implanted lithium 211 from lithium ion beam
210. Vacuum environment 217 can be provided as vacuum
chamber with a selected base pressure or pumping speed.
The vacuum chamber can accommodate reception of a
lithium ion source, communication of lithium ion beam 210
from the lithium ion source, and material for implantation of
lithium ions. The base pressure can be selected to provide a
suitable mean free path of lithium ion beam 210 from the
lithium ion source to a selected target such as electrode
particles, anode 203, cathode 204, and the like.

Electrode particles 219 can be subjected to lithium ion
beam 210 and receive Li+ from lithium ion beam 210 for
disposal of Li+ as ion beam implanted lithium 211. Elec-
trode particles 219 with ion beam implanted lithium 211 can
be subjected to processing to form an electrode (e.g., anode
203 or cathode 204). Electrode particles 219 can include a
silicon, quartz, gallium arsenide, metal, plastic, glass,
ceramic, polymer, and the like. A diameter of electrode
particles 219 can be from 1 nm to 1 cm, specifically from 1
jum to 10 mm, and more specifically from 10 um to 100 um.
A density of ion beam implanted lithium 211 in electrode
particles 219 can be from 0 atoms/em* to 10'° atoms/cm,
specifically from 100 atoms/cm: to 10 atoms/em*, and more
specifically from 1000 atoms/cm? to 10° atoms/cm*.

Compositions can be prepared for making electrodes. In
an embodiment, electrode composition 222 can be disposed
ona member such as a current collector (e.g., anodic current
collector 205 or cathodic current collector 207) to form an
electrode (anode 203 or cathode 204). Electrode composi-
tion 222 can include electrode particles 219, conductive
additive 220, and electrode composition 222. It is contem-
plated that optional additives.

Conductive additive 220 provides electrical conductivity
in electrodes (203, 204) for communication of Li+ through
electrodes. By adding conductive additive 220, lithium ion
conductivity can be increased. Therefore, a conduction path
for lithium ions in electrodes can be provided, and an
internal resistance prelithiated lithium ion battery 200 can be
reduced. As a result, an amount of a current that can flow
through the lithium ion conduction path increases, and
charge-discharge characteristics of prelithiated lithium ion
battery 200 are improved. Conductive additive 220 can
include acetylene black, carbon black, graphite, carbon
fibers, and carbon nanotubes, and the like. A thickness of



US 11,876,211 B2
Page 2

(51) Int. CL.

HOIM 4/04 (2006.01)
HOIM 4/66 (2006.01)
HOIM 4/1395 (2010.01)
HOIM 50/409 (2021.01)
(52) U.S. Cl.
CPC ....... HOIM 4/661 (2013.01); HOIM 10/0525

(2013.01); HOIM 50/409 (2021.01)
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2021/0013490 AL* 1/2021 Lin

OTHER PUBLIC!

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* cited by examiner


US 11,876,211 B2

15

lithium foils, sacrificial additives, donors, or mechanical
mixing with SLMP that causes consumption of lithium for
formation of passivation films or SEI. Through dry, in-vacuo
prelithiation of making prelithiated lithium ion battery 200.
lithium consuming side reactions are decreased or elimi- 5
nated to reduce interfacial impedance in prelithiated lithium.
ion battery 200. Electrode materials prelithiated by injection
of Li* have enhanced stability in dry and ambient air
conditions and under ageing.

Making prelithiated lithium ion battery 200 overcomes
further issues of conventional process, wherein conventional
initial lithiation steps can be done on fully-assembled cells
where there is a fixed amount of lithium. There, a fraction of
Li is consumed in converting the electrode material to a
lithiated state and creating the SEI layer. SEI grows, leading 15
to capacity fading upon cycling of the cell. Making prelithi-
ated lithium ion battery 200 is dry, in-vacuo lithiation that
provides reduction of consumption of lithium and provides
modification of the structure of the electrode materials by
defect engineering during the interactions of implanted Li* 2
with materials that lead to smaller cells and higher energy
densities.

In conventional lithium batteries in a first cycle of opera-
tion, i.e., charge and discharge, Li* and electrons move from
positively charged cathode to negatively charged anode and
in a reverse process for further operation of the battery.
When the potential of the anode is below 1 V vs. Li metal
electrode, organic electrolytes can be reduced on an anode
surface that produces a passivation film layer of SEI. SEI has
astructure and chemical composition that includes inorganic
and organic lithium compounds formed during growth of a
passivation film. The first cycle of a conventional lithium
battery can irreversibly consume, e.g., with graphite anodes,
5 to 20% of Li* that leads to losses of storage capacity and
decreases Coulombic efficiency. Conventional cathodes 3
include mixed lithium transition metal oxides (LiCoO,,
LiMn,O, LiFePO,, LiNiO3, Li[LiNiMn,CoJO,) and can
have relatively low specific capacities that can be less than
300 mAh/g that is less than anodes in prelithiated lithium ion
battery 200. If lithium loading is increased in conventional
cathode material, such loading can reduce specific energy
and energy density of the conventional battery. Beneficially,
prelithiated lithium ion battery 200 overcomes these issues
and fills the need for alternative methods to suppress irre-
versible losses and enhance the first cycle Coulombic efli- 4
ciency as compared with conventional processes. Making
prelithiated lithium ion battery 200 provides high-capacity
prelithiation or pre-compensation of electrodes to compen-
sate irreversible lithium losses that are problems with con-

0

&

ventional Li-based electrochemical energy storage systems. 50
The articles and processes herein are illustrated further by
the following Examples, which are non-limiting.
EXAMPLES,
35
Example 1

Li* implantation depth and lateral distributions for
selected materials can be controlled by energy of Li* (, e.g.
from 0.5 to 100 keV), select ion current, or size or shape of 6
‘an exposed area subjected to lithium ion beam 210. In this
respect, Monte Carlo simulations for a 35-nm thick Si anode
subject to 2 keV and 10 keV Li+ are shown respectively in
FIG. 16 and FIG. 17. Li* doses from 10’° ions/cm? to 10°*
ions/cm? can be controlled by monitoring current received 6:
by, e.g. a Faraday cup. For a three-dimensional (3D) pre-
lithiated lithium ion battery 200, such as a pin-sized inter-

16
digital Li-ion micro battery printed in a 3D pack, spatially-
resolved 3D Li* implantation can be performed in electrode
areas varying by size and shape with low-energy scanning
LiFIB as shown in FIG. 11. FIG. 12 shows exemplary
implantation paths of Li* on implantable areas, e.g., of
cathodic current collector 207 although this applies to other
components of prelithiated lithium ion battery 200 as well.

Example 2

Besides a lithium fast ion bombardment (LiFIB) beam,
dry ion implantation can involve ionic gases of dopants (e.g.,
B, P. As, Sb) accelerated in an electrical field varying from
100 eV up to 10 MeV with injected of such into a semi-
conductor material (e.g., Si, GaAs) under a vacuum of 107°
to 10-7 Torr. At energies below 100 keV, doses can be range
from 10'° up to 10'> ion/em? for an achievable ion current
and up to 10!7 ion/em? with a high current-high dose
implanter. High current-high dose Li* implanters and com-
pact low-energy Li* sources can be overcome these limita-
tions. A cold-atom scanning LiFIB system with a Li* source
(FIG. 18) provides a Li* number density up to 8x10!7
Li*/em?* in selected shapes of a Si membrane (FIG. 19). The

5 implantation area can be subject to flooding Li*, focused Li*

beam, or rastering of Li* beam on a select area of material
subject to lithium ion beam 210. FIG. 19A shows a low-
ification bright field transmission electron microscope
(BF-TEM) image of an annular ion beam implanted lithium
211 for an area in a corner of a 100 umx100 pm, 35 nm-thick
window of <100> c-Si membrane. The bottom inset in FIG,
19A shows ion-induced secondary electron (iSE) image of
the area after implantation in LiFIB. FIG. 19B shows
normalized electron energy-loss (EEL) spectra extracted
from site | and site 2 as marked in annular dark-field (ADO
scanning TEM (STEM) image (inset). EEL spectra show Li
K-edge at 55 eV and the Si, ,-edge at 99 eV energy loss.
FIG. 19C shows Li areal density map for lithium distribu-
tions with Li* concentrations from 0 to 8-10'7 Li*/em?.

While one or more embodiments have been shown and
described, modifications and substitutions may be made
thereto without departing from the spirit and scope of the
invention. Accordingly, it is to be understood that the present
invention has been described by way of illustrations and not
limitation. Embodiments herein can be used independently
or can be combined.

All ranges disclosed herein are inclusive of the endpoints,
and the endpoints are independently combinable with each
other. The ranges are continuous and thus contain every
value and subset thereof in the range. Unless otherwise
stated or contextually inapplicable, all percentages, when
expressing a quantity, are weight percentages. The suffix
“(s)” as used herein is intended to include both the singular
and the plural of the term that it modifies, thereby including
at least one of that term (e.g., the colorant(s) includes at least
one colorants). “Optional” or “optionally” means that the
subsequently described event or circumstance can or cannot
occur, and that the description includes instances where the
event occurs and instances where it does not. As used herein,
“combination” is inclusive of blends, mixtures, alloys, reac-
tion products, and the like.

As used herein, “a combination thereof” refers to a
combination comprising at least one of the named constitu-
ents, components, compounds, or elements, optionally
together with one or more of the same class of constituents,
components, compounds, or elements.

All references are incorporated herein by reference.



U.S. Patent Jan. 16, 2024 Sheet 11 of 19 US 11,876,211 B2

(A) 215
Z 208
t 205
x a10-
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(H)
(G) 213 207 O 5 O © og baany
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FIG. 11


U.S. Patent Jan. 16, 2024 Sheet 14 of 19 US 11,876,211 B2

Fabrication of isolated scaffold structure for 3D batteries (VLS-
growth, thin film deposition, sputtering

- : Controlled Li" implantation far oreation of
(Coating of the back (inner) current collector tayer | b internal Li reservoirs followed by annealing

ee

Coating, deposition & sputtering of thin film high capacity cathode
fayers (LIMO,, M = Co, Ni, Mn}

(Coating, depositian & sputtering of solid electrotyte layer |

(Coating, deposition & sputtering of thin fimiNW for high capacity anodes (Si, carbons) |

Rud

[Pretitiation & mocifcation of anode layers by controlled L? implantation |

Annealing & diffusion (60-600° C)

[Coating of the front (outer) current collector layer | b |

‘Contratied Li" implantation for creation of
internal Li reservoirs

[Anneating of composite electrode ayers | @
iia

FIG. 14