# Patent

## Title
Chemical synthesis route for lithium ion battery applications

## Abstract

An exemplary embodiment of a synthesis method includes the following acts or steps: providing LiMn2O4 material as a precursor; leaching Mn from the LiMn2O4 material using an acid to form a synthesized solution; adding carbonaceous material to the synthesized solution; adding phosphoric acid to the synthesized solution with carbonaceous material to form MnPO4 composite material; and adding Li containing compound to the MnPO4 composite material to form LiMnPO4 composite material.

## Background
TECHNICAL FIELD
The present disclosure is generally concerned with processing techniques for materials synthesis for lithium ion batteries.
BACKGROUND
Conventional LiMnPO4 material is a material exhibiting low electrical conductivity. As a result, this material is restrictive or picky on the synthesis conditions and electrode preparation methods for lithium ion battery applications. Even though carbon coating has been used to improve the electrochemical property, carbon coating alone may not resolve the intrinsically low electrical conductivity nature of the LiMnPO4 material. Furthermore, the carbon coating may limit the storage time of the resultant material, and the coating nature may be destroyed during the slurry making process especially when solvent is water based. Since coating is on the material surface only, the integrity of the coating is always challenged during the electrode making processes and this increases the chance of unstable (inconsistent) performance of the final battery.



BRIEF DESCRIPTION OF THE DRAWINGS
Many aspects of the disclosure can be better understood with reference to the following drawings. The components in the drawings are not necessarily to scale, emphasis instead being placed upon clearly illustrating the principles of certain embodiments of the present disclosure. Moreover, in the drawings, like reference numerals designate corresponding parts throughout the several views.
FIG. 1 is a flow chart diagram illustrating an embodiment of an exemplary process for materials synthesis for lithium ion batteries in accordance with the present disclosure.
FIG. 2 is a diagram of an exemplary embodiment of a furnace and a heat treatment environment for the synthesis of materials in accordance with the present disclosure.
FIGS. 3A-3B are diagrams illustrating results of an examination of synthesized materials using X-ray diffraction in accordance with embodiments of the present disclosure.
FIG. 4 is diagram of examination results for the charge capacity of synthesized materials in accordance with embodiments of the present disclosure.
FIG. 5 is a diagram illustrating a result of an examination of synthesized materials using X-ray diffraction in accordance with embodiments of the present disclosure.



DETAILED DESCRIPTION
Disclosed herein are certain embodiments of a novel chemical synthesis route for lithium ion battery applications. In one such embodiment, battery active material LiMn2O4 is used as a starting precursor. Accordingly, a new synthesis route is disclosed showing how to make LiMnPO4 composite materials at low temperatures using LiMn2O4 as the synthesis precursor. By doing so, a resulting material's electrical conductivity is enhanced with the presence of residual LiMn2O4. Further, with the aid of a synthesis route of phosphate material at low temperatures, it is possible to synthesize materials with dual battery active material, thus achieving the possibility in tailoring physical and electrochemical properties of the synthesized materials. In addition, embodiments of the present disclosure contemplate and allow for multiple-active-material materials systems in battery applications.
In accordance with the present disclosure, spinel structured LiMn2O4 may be used as the precursor material, in various embodiments. Consider that since the spinel structured LiMn2O4 is stable at high temperatures, it is easy to synthesize mixed oxide phosphate material using spinel structure material as the precursor. For example, the synthesis of Li(Mn1/2Fe1/2)PO4 can be achieved using Li(Mn1/2Fe1/2)2O4 as the starting precursor.
Additionally, for various embodiments, control of phosphorous content may determine the ratio of the precursor to the resultant material. This may be useful in tailoring the electrical conductivity as well as the electrochemical capacity of the resultant material. For example, easy control of the phosphorous content in the resultant material renders flexibility in tailoring a final material's physical and electrochemical properties.
As discussed below, an embodiment of a new synthesis route is disclosed showing how to make LiMnPO4 or LiMnPO4—LiMn2O4 composite materials at low temperatures (e.g., less than 400° C., and can be as low as 120° C.) using LiMn2O4 as the synthesis precursor. Low temperature synthesis offers the chance in maintaining the precursor materials structure (and thus maintain electrochemically active) in the resultant material.
In general, an embodiment of a process for the new materials synthesis contains several important steps as shown in FIG. 1. The process starts with the leaching of LiMn2O4 using acids, in step 102. Next, carbonaceous materials that decompose at elevated temperatures are added, in step 104. Here, elevated temperatures are meant to include temperatures which are sufficient in decomposing the carbonaceous materials thus increasing the materials conductivity.
Referring back to the figure, the synthesized material is partially converted to LiMnPO4, in step 106; and a proper amount of Li containing compound is added, in step 108, as discussed further below. Then, the synthesized material is dried using a furnace under air or oxygen atmosphere, in step 110, to produce or generate the resulting material, in step 112.
FIG. 2 shows the design of a furnace and a heat treatment environment for the synthesis of the materials presently disclosed. FIG. 2 shows reaction vessel 1, which is open to air in furnace 2. The furnace is open to the atmosphere at 3a and 3b so as to maintain substantially atmospheric pressure in the furnace. Flow of gases into or out of the furnace is dependent on heating and cooling cycles of the furnace and chemical reactions taking place with materials in the furnace. Air is free to enter the furnace, and air and/or products of a chemical reaction of materials 4 in the reaction vessel 1 are free to exit the furnace. Materials 4 in vessel 1 react chemically during heating steps to form cathode materials in accordance with the present disclosure. Materials 4 in vessel 1, which face air found in the furnace, are covered by a layer of a high temperature inert blanket 5, which is porous to air and escaping gases caused by the heating step. Heating coils of the furnace are indicated at 6.
The following are examples of synthesis routes in accordance with embodiments of the present disclosure.
EXAMPLE 1
Synthesis of LiMnPO4—LiMn2O4=1.8:0.1 in Molar Ratio (Equivalent to 95 mol % of LiMnPO4 and 5 mol % of LiMn2O4)
The overall reaction can be simply described below as:

1LiMn2O4+1.8H3PO4+0.9Li→1.8LiMnPO4+0.1LiMn2O4+(H and O).

Exemplary synthesis procedures are detailed as below:

    
    
        1. Initially, dissolve oxalic acid (e.g., 22.5 g) (0.25 mole) in CMC (carboxymethyl cellulose 1 wt % solution) 40 g at 60° C.
        2. Add LiMn2O4 (e.g., 181 g) (1 mole) to the solution. At this time, purplish foam evolves implying the dissolution of Mn into the solution. Keep the solution at 80° C. for two hours until reaction is completed.
        3. Add proper amount of carbonaceous materials. In this exemplary case, sucrose (e.g., 67.5 g) is added into the solution.
        4. Then, cool down the solution using ice bath.
        5. Then, add phosphoric acid (e.g., 207 g) (1.8 mole, 85% in H3PO4 content) to the solution slowly (in two hours) in ice bath.
        6. Then, warm the solution to 50° C. for two hours (at this moment, greenish powder forms).
        7. Cool the solution again and add (e.g., 50 g) (1.1 mole) formic acid. Afterwards, add Li2CO3 (e.g., 33.3 g) (0.9 mole in Li content) to the solution. While adding Li2CO3 to the solution, bubbles form and the solution became a slurry.
        8. After Li2CO3 addition, the slurry temperature is raised again to 50° C. At this time, foaming is observed.
        9. After 2 hours foaming, the very viscous solution is dried at 120° C. for 10 hours.
    
    


Step 1 and 2 (above) are used for leaching Mn from LiMn2O4. The acid used in step 1 is not limited to oxalic acid. Formic acid, acetic acid, hydrochloric acid, nitric acid are all allowed. However, organic acids are preferred in some embodiments.
Step 3 (above) is used in carbonaceous material addition. The carbonaceous material is not limited to sucrose. Methyl cellulose (MC), Methylcarboxylmethyl cellulose (CMC), Cellulose acetate, starch, styrene butadiene rubber are all allowed in achieving the same goal (i.e. increase material's electrical conductivity after decomposition). In fact, the materials synthesis can be free from the addition of the carbonaceous material if proper amount and distribution of LiMn2O4 are present in the resultant material.
Steps 4, 5, and 6 (above) are used for MnPO4 formation. These steps control the percentage of LiMn2O4 remaining or the percentage of MnPO4 formation. Steps 7, 8, and 9 are used for the formation of LiMnPO4 in the form of foam. Foaming can be helpful in making materials with open porosity.
For comparative analysis, the resultant material was examined with XRD (X-ray Diffraction) and the XRD result is shown in FIGS. 3A-3B. Rietveld refinement was conducted on the XRD result using space group Pmnb(62). The lattice parameters were determined to be a=6.10287, b=10.4603, and c=4.74375 with cell volume=302.8 (Å3) and Density=3.4401 g/cm3. In this case, the trace phase of LiMn2O4 is not obvious in the XRD plot. The particle size and BET analyses on the precursor LiMn2O4 and the resultant material are also shown in Table I for comparisons of the evolution of physical properties exhibited by the material during the synthesis route.













TABLE I













Surface Area












Particle size Data (um)
Data (BET)














D10
D50
D100
(m2/g)

















LiMn2O4
2.88
15.97
71.08
0.6368



Resultant
0.78
2.39
44.60
1.2556



Material †







After Heat
0.86
2.81
60.03
2.35



Treatment ‡











† Resultant material was obtained after drying the sample at 120° C. for 10 hours.



‡ After heat treatment refers to 260° C. for 2 hours.






From Table I, it can be seen that pulverization of the precursor material occurred during the synthesis. The particle size decreased with the increase of specific surface area. A further heat treatment of the resultant material at 260° C. for 2 hours in air shows that a moderate increase of particle size is accompanied with significant increase of specific surface area (please refer to Table 1). This result indicates that sintering of the material is not rigorous at 260° C. but the decomposition of the carbonaceous material is contributing to the significant increase of the specific surface area. It should be noticed that the decomposition at 260° C. could help material's electrical conductivity owing to the presence of the electrical conducting carbon resulted from the carbonaceous materials decomposition.
EXAMPLE 2
Electrochemical Characterization of LiMnPO4—LiMn2O4=1.8:0.1 in Molar Ratio (Equivalent to 95 mol % of LiMnPO4 and 5 mol % of LiMn2O4)
For electrode preparation, 5 g of active material, 1 g of Super-P carbon black, and 0.3 g of SBR (styrene-butadiene rubber) are used in the slurry making. After coating using doctor blade, the coated electrode is dried at 110° C. for 3 hours followed by punching of the electrode. After vacuum drying again at 110° C. for overnight, the electrodes are transferred to the glove box for test cell assembly. The test cell is a three-electrode design with Li as the reference electrode. The electrode loading is 6 mg and the active material content is 81.3%. The C-rate used is around C/10 and the room temperature is around 23° C.
A charge capacity of 160.5 mAh/g and a discharge capacity of 51 mAh/g are obtained, as shown in the examination results of FIG. 4. The corresponding Coulomb efficiency is observed to be 31.7%. Since the test cell was charged to 4.9V, more or less decomposition of the electrolyte during charging could result in the low Coulomb efficiency.
EXAMPLE 3
Synthesis of LiMnPO4—LiMn2O4=1:0.5 in Molar Ratio (Equivalent to 67 mol % of LiMnPO4 and 33 mol % of LiMn2O4)
The overall reaction can be simply described below as:

1LiMn2O4+1H3PO4→1Li(1-0.5x)MnPO4+0.5LixMn2O4,

where X represents deficiency of Li. Exemplary synthesis procedures are detailed as below:

    
    
        1. Initially, dissolve oxalic acid (e.g., 11.25 g) (0.125 mole) in CMC (carboxymethyl cellulose 1 wt % solution) (e.g., 40 g) at 80° C.
        2. Add LiMn2O4 (e.g., 90.5 g) (0.5 mole) to the solution. At this time, purplish foam evolves implying the dissolution of Mn into the solution. Keep the solution at 80° C. for two hours until reaction is completed.
        3. Add proper amount of carbonaceous materials. In this exemplary case, sucrose (e.g., 33.75 g) is added into the solution.
        4. Then, cool down the solution using ice bath.
        5. Then, add phosphoric acid (e.g., 57.65 g) (0.5 mole, 85% in H3PO4 content) to the solution slowly (in two hours) in ice bath.
        6. Then, warm the solution to 50° C. for two hours (at this moment, greenish powder forms).
        7. Wait until the solution become tacky.
        8. Conduct heat treatment by sending the precursor material directly to the furnace at 380° C. for 10 hours under oxygen.
    
    


For comparative analysis, the resultant material was examined with XRD and the XRD result is shown in FIG. 5. From the XRD result, it can be identified that the resultant material consists of two phases (LiMnPO4 and LiMn2O4 co-exist), which are present simultaneously.
Until this point, it is clear that the low temperature synthesis in accordance with embodiments of the present disclosure allows the co-existence of LiMnPO4 and LiMn2O4. The electrochemical data reveals the potential in synthesizing LiMnPO4 with the presence of LiMn2O4 using LiMn2O4 as the starting precursor. Advantageously, the presence of LiMn2O4 in the LiMnPO4/LiMn2O4 composite material provides electrochemical activity as well as the electrical conducting capability in the composite material. Exemplary composite material for lithium ion battery applications in accordance with the present disclosure may be in the form of (x)LiMnPO4/(1−x)LiMn2O4, where x ranges from 0.67 mol % to 0.99 mol %.
Any process descriptions or blocks in flow charts should be understood as representing steps in an exemplary process, and alternate implementations are included within the scope of the disclosure in which steps may be executed out of order from that shown or discussed, including substantially concurrently or in reverse order, depending on the functionality involved, as would be understood by those reasonably skilled in the art of the present disclosure.
It should be emphasized that the above-described embodiments are merely possible examples of implementations, merely set forth for a clear understanding of the principles of the disclosure. Many variations and modifications may be made to the above-described embodiment(s) without departing substantially from the spirit and principles of the disclosure. All such modifications and variations are intended to be included herein within the scope of this disclosure and protected by the following claims.

## Claims

1. A synthesis method comprising:
providing LiMn2O4 material as a precursor;
leaching Mn from the LiMn2O4 material using an organic acid to form a synthesized solution;
adding carbonaceous material as part of the synthesized solution; and
adding phosphoric acid as part of the synthesized solution with carbonaceous material to form LiMnPO4—LiMn2O4 composite material.

2. The method of claim 1, wherein the carbonaceous material comprises one of sucrose, methyl cellulose, methylcarboxylmethyl cellulose (CMC), cellulose acetate, starch, or styrene butadiene rubber.

3. The method of claim 1, further comprising:
after adding the carbonaceous material, cooling down the synthesized material with carbonaceous material as a part, wherein the phosphoric acid is added while the synthesized material is still cooled.

4. The method of claim 1, further comprising:
drying the LiMnPO4—LiMn2O4 composite material using a furnace under air or oxygen atmosphere.

5. The method of claim 4, wherein a temperature of the furnace does not exceed 400° C.

6. The method of claim 4, wherein a further heat treatment after drying does not exceed 400° C.

7. The method of claim 1, further comprising:
after adding the phosphoric acid, heating the LiMnPO4—LiMn2O4 composite material to produce foaming.

8. The method of claim 1, further comprising:
after adding phosphoric acid as part of the synthesized solution with carbonaceous material to form LiMnPO4—LiMn2O4 composite material, heating the synthesized material with carbonaceous material at or below approximately 400° C. for approximately 2 hours to aid in decomposition of the carbonaceous material.