Source: https://patents.google.com/patent/US7939049?oq=5%2C266%2C072
Timestamp: 2018-03-21 21:07:40
Document Index: 145993255

Matched Legal Cases: ['Application No. 095116589', 'Application No. 200780002216', 'Application No. 200780002227', 'Application No. 200780002247', 'Application No. 200780002247', 'Application No. 095116589', 'Art. 115', 'Art. 115', 'Art. 115']

US7939049B2 - Cathode material containing Ni-based lithium transition metal oxide - Google Patents
Cathode material containing Ni-based lithium transition metal oxide Download PDF
US7939049B2
US7939049B2 US12378899 US37889909A US7939049B2 US 7939049 B2 US7939049 B2 US 7939049B2 US 12378899 US12378899 US 12378899 US 37889909 A US37889909 A US 37889909A US 7939049 B2 US7939049 B2 US 7939049B2
US12378899
US20090224215A1 (en )
Jens M. Paulsen
M′=Ni1−a−b(Ni1/2Mn1/2)aCob on condition of 0.65≦a+b≦0.85 and 0.1≦b≦0.4;
A is a dopant;
0≦k≦0.05; and
x+y=2 on condition of 0.95≦x≦1.05.
Comparative Example 1 pH Titration of Li2CO3 Impurity in Commercial Cathode Materials
Comparative Example 2 Thermodynamic Stability of Commercial High-Ni LiNiO2
In this experiment, the thermodynamic stability of commercial LiNiO2 was investigated. The sample had the composition of LiNi0.8Co0.1Mn0.1O2 which may be alternatively expressed as LiNi1−xMxO2 with x=0.3, i.e., M=Mn1/3Ni1/3Co1/3.
Comparative Example 3 Li2CO3 Impurity in Commercial High-Ni LiNiO2
In this experiment, it was investigated whether the stoichiometric and impurity-free high-Ni LiNiO2 can be obtained on a large scale by a simple process involving solid state reaction in oxygen.
Comparative Example 4 Air Stability of Commercial High-Ni LiNiO2
The pH titration result of commercial high-Ni LiNiO2 before and after exposure to humid air is shown in FIG. 6. The commercial LiNiO2 is LiAl0.02Ni0.78Co0.2O2, additionally containing less than 1% of barium compounds, and the results of FIG. 6 show that the amount of soluble base before storage is exceptionally low. It is expected that the producer has prepared the sample in oxygen, either from extremely pure (i.e., CO3 anion-free) precursors or by applying at least two cooking steps, interrupted by a washing procedure to remove Li2CO3 and LiOH impurities. Barium is probably added to trap the remaining CO3 anions by forming the highly stable BaCO3. This manner is a high-cost process.
Comparative Example 5 Air Stability of Commercial Coated High-Ni LiNiO2
Another commercial high-Ni LiNiO2 sample with the composition of LiNi0.8Mn0.05Co0.15O2 was tested. The preparation process of the sample includes a surface coating by AlPO4, followed by a mild heat treatment, and this is a high cost process. The coating is probably a dip-coating process, having the side effect that excess Li2CO3 is dissolved. Furthermore, during the heat treatment, AlPO4 reacts with excess lithium so that Li3PO4 and Al2O3 (or LiAlO2) can form. Therefore, the sample has a low content of Li2CO3 and the surface of the cathode material is lithium-deficient. The experimental results confirmed a reduced swelling property in polymer cells. By the pH titration result, a low initial Li2CO3 content (12 ml 0.1M HCl per 10 g cathode) was ascertained. The profile was very similar to that of the fresh sample of Comparative Example 4, Curve (A). Two more pH profiles were recorded after storage in a humidity chamber similar to Comparative Example 4. Only a slightly lower formation rate of Li2CO3 (80˜90%) compared with Comparative Example 4 was observed.
Comparative Example 6 Safety of Commercial High-Ni LiNiO2
The result of DSC measurement is shown in FIG. 7. For the measurement, coin cells (Li metal anode) with LiNiO2 cathodes were charged to 4.3 V, and after disassembly they were inserted into hermetically sealed DSC cans, and electrolyte was poured thereinto. The total amount of cathode was about 50˜60 mg and the amount of electrolyte was approximately the same. As such, the exothermic reaction is strongly cathode-limited (only a fraction of the electrolyte can be fully combusted by all oxygen of the cathode). The DSC measurement was performed at a heat rate of 0.5 K/min.
Comparative Example 7 Electrochemical Properties of Commercial High-Ni LiNiO2
In Table 1 below, the results of electrochemical testing of different commercial high-Ni LiNiO2 materials are summarized. The testing was performed at 60° C. at C/5 charge and discharge rate. The charge voltage was 4.3 V. Referring to Table 1, with the exception of Sample (B), the cycling stability is poor. The poor cycling stability of Sample (C) is probably caused by the Li-deficiency of the surface (the poor capacity retention of cation-mixed (i.e., Li-deficient) lithium nickel oxides is known in the prior art literatures). Both Samples (A) and (B) are stoichiometric (i.e., not Li-deficient), but only Sample (B) has a low content of Li2CO3. The presence of Li2CO3 may not only cause gassing but also fading (Probably at 4.3 V, Li2CO3 slowly decomposes and the crystallites lose electrical contact).
(A) (B) Al/Ba-
LiNi0.8Co0.2O2 modified (C) AlPO4-coated
Described in Comp. Ex. 3 Comp. Ex. 4 Comp. Ex. 5
Stoichiometry Stoichiometric Stoichiometric Surface Li
Li:M high low deficient
Capacity at 193, 175 mAh/g 195, 175 mAh/g 185, 155 mAh/g
Capacity loss 30% per 100 11% per 100 >30% per 100
Comparative Example 8 Volumetric Capacity of Commercial Low-Ni LiNiO2
Commercial LiMO2 with M=(Ni1/2Mn1/2)1−xCox with x=0.17 and with x=0.33, respectively, were tested. The crystallographic densities thereof were approx. 4.7 and 4.76 g/cm3, respectively. A discharge capacity of 157˜159 mAh/g at C/10 rate (3˜4.3 V) was obtained for both materials.
Example 1 Sintering Stability
(A) 850° C. (B) 900° C. (C) 950° C. (D) 1000° C.
Unit cell 33.902 Å3 33.905 Å3 33.934 Å3 33.957 Å3
Normalized c:a 1.0123 1.0124 1.0120 1.0117
Cation mixing 4.5% 3.9% 4.3% 4.5%
Comparative Example 9 Sintering Stability of High Co Samples
(A) 900° C. (B) 950° C. (C) 1000° C.
Unit cell volume 33.445 Å3 33.457 Å3 33.514 Å3
Normalized c:a 1.0144 1.0142 1.0154
Cation mixing from 3.3% 6.3% 6.6%
Example 2 Li Stoichiometric Range
Desired 0.925 0.975 1.0 1.025 1.05 1.075 1.125
Unit cell 34.110 Å3 34.023 Å3 33.968 Å3 33.921 Å3 33.882 Å3 33.857 Å3 33.764 Å3
c:a ratio 1.0117 1.0119 1.0119 1.0122 1.0122 1.0123 1.0125
Cation 8.8% 6.6% 6.7% 4.0% 2.1% 2.5% 1.4%
Example 3 Large-Scale Sample Prepared in Air Using Li2CO3
Approx. 5 kg of LiMO2 was prepared in one batch. Precursors were Li2CO3 and a mixed hydroxide MOOH with M=Ni4/15(Mn1/2Ni1/2)8/15Co0.2. The preparation process involved 3 cooking steps. By heating to 700° C., a precursor with a Li:M ratio of approx. 1:1 was prepared. The furnace was a chamber furnace of about 20 liter volume; the sample was located in a tray of high-temperature steel. This precursor was sintered at 900° C. for 10 hours. During the sintering, air was pumped into the furnace. More than 10 m3 of air was fed into the oven during sintering for 10 hours. After the sintering, the unit cell constant was obtained by X-ray analysis, and the unit cell volume was compared with the target value. The target value was the unit cell volume of the sample in Example 2 which had the best electrochemical properties. pH titration of the sintered sample showed a profile very similar to that of Sample (E) in Example 2, which proves that the 5 kg sample was basically free of Li2CO3 impurity. A small amount of Li2CO3 was added to ensure that the targeted unit cell volume is achieved after the final sintering. The final cooking was performed in air at 900° C.
Comparative Example 10 No Air Pumping
Example 4 Heat Exchanger
Example 5 Coin cell testing of Large-Scale Sample
Electrochemical properties of LiNiO2
(extrapolated) after 1st charge
100 cycles C/5-C/5 capacity discharge capacity
cycling, 3.0-4.3 V 3.0-4.3 V, 25° C., 25° C., 60° C.,
25° C. 60° C. C/10 C/1 C/20 C/20
>96% >90% >190 152 173 185
mAh/g mA/g mAh/g mAh/g
Example 6 DSC of Large-Scale Sample
Example 7 Polymer Cell of Large-Scale Sample
FIG. 15 shows the cycling stability (0.8 C charge, 1 C discharge, 3˜4 V, 2 V) at 25° C.
An exceptional cycling stability (91% at C/1 rate after 300 cycles) was achieved at room temperature. The build-up of impedance was low. The cycling stability exceeds that of a similar LiCoO2 cell. This can be explained by the comparable, large irreversible capacity of the high-Ni LiNiO2, additionally supplying lithium which is consumed during cycling at the anode SEI.
Example 8 Air stability of Large-Scale Sample
Example 9 Inexpensive Transition Metal Precursors
Example 10 Reproducibility of pH Titration
US12378899 2005-04-13 2009-02-20 Cathode material containing Ni-based lithium transition metal oxide Active US7939049B2 (en)
US11104734 US7648693B2 (en) 2005-04-13 2005-04-13 Ni-based lithium transition metal oxide
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US12378946 Active 2025-06-22 US7943111B2 (en) 2005-04-13 2009-02-20 Process of making cathode material containing Ni-based lithium transition metal oxide
US13077052 Active 2025-05-16 US8574541B2 (en) 2005-04-13 2011-03-31 Process of making cathode material containing Ni-based lithium transition metal oxide
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