CN102694178B - The positive electrode, battery and preparation method thereof of battery - Google Patents
The positive electrode, battery and preparation method thereof of battery Download PDFInfo
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- CN102694178B CN102694178B CN201210205962.1A CN201210205962A CN102694178B CN 102694178 B CN102694178 B CN 102694178B CN 201210205962 A CN201210205962 A CN 201210205962A CN 102694178 B CN102694178 B CN 102694178B
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- system battery
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims abstract description 26
- 229910013716 LiNi Inorganic materials 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 12
- 230000008859 change Effects 0.000 claims abstract description 8
- 230000037452 priming Effects 0.000 claims abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 7
- 230000000996 additive effect Effects 0.000 claims abstract description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 10
- 239000003337 fertilizer Substances 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 2
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 22
- 238000004080 punching Methods 0.000 description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 239000006230 acetylene black Substances 0.000 description 10
- 238000011056 performance test Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- 239000002033 PVDF binder Substances 0.000 description 9
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 9
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- -1 ethyl carbonate ester Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910016118 LiMn1.5Ni0.5O4 Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a kind of positive electrode of battery, LiNi
0.5mn
1.5o
4/ C system battery and preparation method thereof, belongs to technical field of lithium ion, and it can solve the problem that existing battery in use exists gassing phenomenon.The positive electrode of battery of the present invention comprises following material: the mass fraction accounting for positive electrode total amount be 0.5%-2% press down gas additive.The generation that gas additive can suppress gassing phenomenon to a certain extent should be pressed down.LiNi of the present invention
0.5mn
1.5o
4the positive electrode of/C system battery adopts above-mentioned positive electrode.LiNi of the present invention
0.5mn
1.5o
4adopt priming procedure in the preparation process of/C system battery and change into step, also suppressing the generation of gassing phenomenon to a certain extent, change into the cell thickness obtained and obviously reduce.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of positive electrode of battery, containing the LiNi of this positive electrode
0.5mn
1.5o
4/ C system battery and preparation method thereof.
Background technology
Lithium ion battery, because high, the good cycle of its energy density, the advantage such as environment friendly and pollution-free, be it is believed that it is the first-selected power of new-energy automobile.In current commercial lithium-ion battery system, LiCoO
2battery, due to expensive, poor stability, is not suitable for using in electric automobile.LiMn
2o
4battery due to shortcomings such as high-temperature behavior differences, and limits its application in electric automobile.LiFePO
4also there is processing characteristics and the shortcoming such as high rate performance, poor performance at low temperatures in battery.Spinel-type LiNi
0.5mn
1.5o
4the advantages such as it is high that positive electrode has operating voltage, low price, are considered to the first-selected positive electrode of lithium-ion-power cell of new generation.Therefore, with LiNi
0.5mn
1.5o
4battery for positive electrode becomes the first-selected power supply of electric automobile.But at LiNi
0.5mn
1.5o
4/ C system battery also exists the phenomenon of gassing, and what this phenomenon was serious have impact on LiNi
0.5mn
1.5o
4the cycle performance of/C system battery, security performance and high rate performance etc.
Summary of the invention
In use there is the problem of gassing phenomenon in the positive electrode that the object of the invention is to solve existing battery, provides a kind of positive electrode of battery.
Solve the positive electrode that technical scheme that the technology of the present invention problem adopts is a kind of battery, comprise following material: the mass fraction accounting for positive electrode total amount be 0.5%-2% press down gas additive.
It is preferably, described that to press down gas additive be Li
2cO
3, one or both mixing in LiOH.
Another object of the present invention solves existing LiNi
0.5mn
1.5o
4/ C system battery also exists the problem of the phenomenon of gassing, provides a kind of LiNi
0.5mn
1.5o
4/ C system battery.
The technical scheme that solution the technology of the present invention problem adopts is a kind of LiNi
0.5mn
1.5o
4/ C system battery, described LiNi
0.5mn
1.5o
4the positive electrode of/C system battery adopts the positive electrode of above-mentioned battery.
For solving problem of the present invention, the present invention also provides a kind of LiNi
0.5mn
1.5o
4the preparation method of/C system battery.
The technical scheme that solution the technology of the present invention problem adopts is a kind of LiNi
0.5mn
1.5o
4the preparation method of/C system battery, comprises the steps:
Priming procedure): to the LiNi completing fluid injection
0.5mn
1.5o
4/ C system battery, in the environment of 40 DEG C-55 DEG C, rushes in advance;
Change into step): the LiNi that priming procedure is obtained
0.5mn
1.5o
4/ C system battery, in the environment of 40 DEG C-55 DEG C, changes into.
Preferably, in described priming procedure: pre-punching degree is that 0.05C charges in 0.02C charging, and 0.1C charges, and shelves 12-20h after completing.
Further preferably, the charging interval of 2-4h, 0.1C charging that to be the charging interval of 3-5h, 0.05C charging be the described charging interval in 0.02C charging is 3-6h.
Preferably, described changes in step: fertilizer alleviant is 0.1C discharge and recharge, 0.2C discharge and recharge, 0.3C discharge and recharge.
Further preferably, the described number of times in 0.1C discharge and recharge is 1-3 time, and the number of times of 0.2C discharge and recharge is 3-5 time, and the number of times of 0.3C discharge and recharge is 2-3 time.
The present invention passes through at LiNi
0.5mn
1.5o
4what the positive pole of/C system battery added 0.5%-2% presses down gas additive, can suppress the generation of gassing phenomenon to a certain extent.
Simultaneously at LiNi
0.5mn
1.5o
4adopt above-mentioned priming procedure in the preparation process of/C system battery and change into step, also suppressing the generation of gassing phenomenon to a certain extent, change into the cell thickness obtained and obviously reduce.
Accompanying drawing explanation
Fig. 1 is LiNi prepared by comparative example of the present invention
0.5mn
1.5o
4battery outside drawing.
Fig. 2 is LiNi prepared by the embodiment of the present invention 5
0.5mn
1.5o
4battery outside drawing.
Embodiment
For making those skilled in the art understand technical scheme of the present invention better, below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Comparative example
This comparative example provides a kind of LiNi
0.5mn
1.5o
4/ C system battery.
Positive electrode forms:
This LiNi
0.5mn
1.5o
4the positive pole of/C system battery is made up of the material of following mass fraction: the LiNi of 92%
0.5mn
1.5o
4, the acetylene black of 4%, the Kynoar (PVDF) of 4%.
Preparation method:
By above-mentioned LiMn
1.5ni
0.5o
4, acetylene black and Kynoar mix, and uses NMP(1-N-methyl-2-2-pyrrolidone N-) this mixture is modulated into slurry, lithium ion battery production technology conveniently, through coating, dry, prick film, cut and be made into based lithium-ion battery positive plate.
With the pole piece of above-mentioned preparation for positive pole, Delanium is negative pole, the LiPF of electrolyte to be concentration be 1.5mol/L
6eC(ethyl carbonate ester) solution+DMC(dimethyl carbonate) solution, its solvent is EC(ethyl carbonate ester)+DMC(dimethyl carbonate), wherein EC(ethyl carbonate ester) and DMC(dimethyl carbonate) volume ratio be 1: 1, barrier film is celgard2400 film, adopts the method for winding to assemble 055065 type LiNi
0.5mn
1.5o
4/ C system battery.At ambient temperature is 25 DEG C, rush in advance night to battery note in the glove box being full of argon gas atmosphere.
The method of pre-punching is: 0.2CmA constant current charge is to 4.90V, and prescribe a time limit 150min.
Change into after completing preliminary filling, the method changed into is:
1) after 0.5CmA constant current charge to 4.9V, turn 4.9V constant voltage charge, cut-off current is 0.05CmA, 120 minutes in limited time;
2) 10min is left standstill;
3) 0.5CmA constant-current discharge is to 3.5V, 150 minutes in limited time;
4) 10min is left standstill;
5) after 1.0CmA constant current charge to 4.9V, turn 4.9V constant voltage charge, cut-off current is 0.05CmA, 120 minutes in limited time;
6) 10min is left standstill;
7) 1.0CmA constant-current discharge is to 3.5V, 100 minutes in limited time;
8) 10min is left standstill;
9) 1.0CmA constant current charge is to 4.5V, in limited time 45min; Then turn 4.5V constant voltage charge, cut-off current is 0.01CmA, in limited time 120min;
10) stop;
After changing into, the gas in aluminum-plastic composite membrane is extracted out, after heat-sealing, obtain product.
This comparative example prepares the performance test data of battery and cell thickness test data in table 1.
The outside drawing of battery prepared by the present embodiment is Fig. 1, visible, and its outward appearance has obvious gassing hollowing phenomenon.
Embodiment 1
The present embodiment provides a kind of LiNi
0.5mn
1.5o
4/ C system battery.
Positive electrode forms:
The positive electrode of this battery is made up of the material of following mass fraction: the LiNi of 91%
0.5mn
1.5o
4, the acetylene black of 4%, the Kynoar (PVDF) of 4%, the Li of 1%
2cO
3.
Preparation method: identical with the method for comparative example.
The present embodiment prepares the performance test data of battery and cell thickness test data in table 1, and visible, compared with the battery that comparative example is obtained, the performance of its battery increases, the thickness of battery obviously reduces.
Embodiment 2
The present embodiment provides a kind of LiNi
0.5mn
1.5o
4/ C system battery.
Positive pole forms:
The positive pole of this battery is made up of the material of following mass fraction: the LiNi of 91.5%
0.5mn
1.5o
4, the acetylene black of 4%, the Kynoar (PVDF) of 4%, the LiOH of 0.5%.
Preparation method: identical with the method for comparative example.
The present embodiment prepares the performance test data of battery and cell thickness test data in table 1, and visible, compared with the battery that comparative example is obtained, the performance of its battery increases, the thickness of battery obviously reduces.
Embodiment 3
The present embodiment provides a kind of LiNi
0.5mn
1.5o
4/ C system battery.
Positive pole forms:
The positive pole of this battery is made up of the material of following mass fraction: the LiNi of 90%
0.5mn
1.5o
4, the acetylene black of 4%, the Kynoar (PVDF) of 4%, the LiOH of 1%, the Li of 1%
2cO
3.
Preparation method: identical with the method for comparative example.
The present embodiment prepares the performance test data of battery and cell thickness test data in table 1, and visible, compared with the battery that comparative example is obtained, the performance of its battery increases, the thickness of battery obviously reduces.
Embodiment 4
The present embodiment provides a kind of LiNi
0.5mn
1.5o
4/ C system battery.
Positive pole forms:
The positive pole of this battery is made up of the material of following mass fraction: the LiNi of 90%
0.5mn
1.5o
4, the acetylene black of 4%, the Kynoar (PVDF) of 4%, the LiOH of 1.5%.
Preparation method: identical with the method for comparative example.
The present embodiment prepares the performance test data of battery and cell thickness test data in table 1, and visible, compared with the battery that comparative example is obtained, the performance of its battery increases, the thickness of battery obviously reduces.
Embodiment 5
The present embodiment provides a kind of LiNi
0.5mn
1.5o
4/ C system battery.
Positive pole forms:
The positive pole of this battery is made up of the material of following mass fraction: the LiNi of 92%
0.5mn
1.5o
4, the acetylene black of 4%, the Li of the Kynoar (PVDF) 1% of 4%
2cO
3.
Preparation method: similar to the method for comparative example, unlike:
Pre-punching method is: be 55 DEG C in ambient temperature, and pre-punching degree is that 0.02C fills 3h, and 0.05C fills 4h, and 0.1C fills 5h.14h is shelved after pre-punching.
Chemical synthesizing method is: ambient temperature is 40 DEG C, and fertilizer alleviant is 0.1C charge and discharge 1 time, 0.2C charge and discharge 4 times, 0.3C charge and discharge 2 times.
The present embodiment prepares the performance test data of battery and cell thickness test data in table 1, and visible, compared with the battery that comparative example is obtained, the performance of its battery increases, the thickness of battery obviously reduces.
The outward appearance that the present embodiment prepares battery is shown in Fig. 2, visible, and obtain battery through preliminary filling compared with battery obtained in comparative example with changing into, its surfacing is without gassing hollowing phenomenon.
Embodiment 6
The present embodiment provides a kind of LiNi
0.5mn
1.5o
4/ C system battery.
Positive pole forms:
The positive pole of this battery is made up of the material of following mass fraction: the LiNi of 92%
0.5mn
1.5o
4, the acetylene black of 4%, the Li of the Kynoar (PVDF) 1% of 4%
2cO
3.
Preparation method: similar to the method for comparative example, unlike:
Pre-punching method is: be 45 DEG C in ambient temperature, and pre-punching degree is that 0.02C fills 4h, and 0.05C fills 2h, and 0.1C fills 4h.20h is shelved after pre-punching.
Chemical synthesizing method is: ambient temperature is 45 DEG C, and fertilizer alleviant is 0.1C charge and discharge 3 times, 0.2C charge and discharge 3 times, 0.3C charge and discharge 2 times.
The present embodiment prepares the performance test data of battery and cell thickness test data in table 1, and visible, the battery obtained with comparative example, the performance of its battery increases, the thickness of battery obviously reduces.
Embodiment 7
The present embodiment provides a kind of LiNi
0.5mn
1.5o
4/ C system battery.
Positive pole forms:
The positive pole of this battery is made up of the material of following mass fraction: the LiNi of 92%
0.5mn
1.5o
4, the acetylene black of 4%, the Li of the Kynoar (PVDF) 1% of 4%
2cO
3.
Preparation method: similar to the method for comparative example, unlike:
Pre-punching method is: be 50 DEG C in ambient temperature, and pre-punching degree is that 0.02C fills 5h, and 0.05C fills 2h, and 0.1C fills 6h.12h is shelved after pre-punching.
Chemical synthesizing method is: ambient temperature is 50 DEG C, and fertilizer alleviant is 0.1C charge and discharge 2 times, 0.2C charge and discharge 5 times, 0.3C charge and discharge 3 times.
The present embodiment prepares the performance test data of battery and cell thickness test data in table 1, and visible, the battery obtained with comparative example, the performance of its battery increases, the thickness of battery obviously reduces.
Embodiment 8
The present embodiment provides a kind of LiNi
0.5mn
1.5o
4/ C system battery.
Positive pole forms: the positive pole of this battery is made up of the material of following mass fraction: the LiNi of 92%
0.5mn
1.5o
4, the acetylene black of 4%, the Li of the Kynoar (PVDF) 1% of 4%
2cO
3.
Preparation method: similar to the method for comparative example, unlike:
Pre-punching method is: be 40 DEG C in ambient temperature, and pre-punching degree is that 0.02C fills 4h, and 0.05C fills 3h, and 0.1C fills 3h.18h is shelved after pre-punching.
Chemical synthesizing method is: ambient temperature is 55 DEG C, and fertilizer alleviant is 0.1C charge and discharge 1 time, 0.2C charge and discharge 5 times, 0.3C charge and discharge 3 times.
The present embodiment prepares the performance test data of battery and cell thickness test data in table 1, and visible, the battery obtained with comparative example, the performance of its battery increases, the thickness of battery obviously reduces.
Table 1 embodiments of the invention prepare performance test data and the cell thickness test data of battery
| Comparative example | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | |
| Specific capacity (mAh/g) | 125 | 128 | 129 | 130 | 131 | 131 | 132 | 135 | 133 |
| 100 capability retentions (%) | 91.5 | 95.6 | 95.8 | 96.2 | 96.5 | 97.0 | 97.2 | 97.3 | 97.5 |
| Change into rear cell thickness (mm) | 8.2 | 5.3 | 5.28 | 5.26 | 5.25 | 5.22 | 5.21 | 5.23 | 5.20 |
Be understandable that, the illustrative embodiments that above execution mode is only used to principle of the present invention is described and adopts, but the present invention is not limited thereto.For those skilled in the art, without departing from the spirit and substance in the present invention, can make various modification and improvement, these modification and improvement are also considered as protection scope of the present invention.
Claims (4)
1. a LiNi
0.5mn
1.5o
4the preparation method of/C system battery, is characterized in that, comprise the steps:
Priming procedure: to the LiNi completing fluid injection
0.5mn
1.5o
4/ C system battery, in the environment of 40 DEG C-55 DEG C, carries out preliminary filling;
Change into step: the LiNi that priming procedure is obtained
0.5mn
1.5o
4/ C system battery, in the environment of 40 DEG C-55 DEG C, changes into, and described changes in step: fertilizer alleviant is 0.1C discharge and recharge, 0.2C discharge and recharge, 0.3C discharge and recharge,
Wherein, described LiNi
0.5mn
1.5o
4the positive electrode of/C system battery comprises following material: the mass fraction accounting for positive electrode total amount be 0.5%-2% press down gas additive, it is described that to press down gas additive be Li
2cO
3, one or both mixing in LiOH.
2. LiNi as claimed in claim 1
0.5mn
1.5o
4the preparation method of/C system battery, is characterized in that, in described priming procedure: pre-charge conditions is that 0.05C charges in 0.02C charging, and 0.1C charges, and shelves 12-20h after completing.
3. LiNi as claimed in claim 2
0.5mn
1.5o
4the preparation method of/C system battery, is characterized in that, the charging interval of 2-4h, 0.1C charging that the described charging interval in 0.02C charging, to be charging interval of 3-5h, 0.05C charging be is 3-6h.
4. LiNi as claimed in claim 1
0.5mn
1.5o
4the preparation method of/C system battery, is characterized in that, the described number of times in 0.1C discharge and recharge is 1-3 time, and the number of times of 0.2C discharge and recharge is 3-5 time, and the number of times of 0.3C discharge and recharge is 2-3 time.
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| CN103151569B (en) * | 2013-03-19 | 2015-07-15 | 奇瑞汽车股份有限公司 | Method for improving cyclical stability of lithium ion battery containing positive material LiNi0.5Mn1.5O4 and lithium ion battery |
| FR3020181B1 (en) * | 2014-04-17 | 2016-04-01 | Renault Sas | METHOD FOR FORMING LI-ION BATTERY CELL COMPRISING LNMO-BASED CATHODE MATERIAL |
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| Publication number | Publication date |
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| CN102694178A (en) | 2012-09-26 |
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