CN110658473B - Method for evaluating storage performance of lithium ion battery anode material - Google Patents
Method for evaluating storage performance of lithium ion battery anode material Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 abstract description 8
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- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
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- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- 229910013191 LiMO2 Inorganic materials 0.000 description 1
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- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R31/00—Arrangements for testing electric properties; Arrangements for locating electric faults; Arrangements for electrical testing characterised by what is being tested not provided for elsewhere
- G01R31/36—Arrangements for testing, measuring or monitoring the electrical condition of accumulators or electric batteries, e.g. capacity or state of charge [SoC]
- G01R31/385—Arrangements for measuring battery or accumulator variables
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Abstract
The invention provides a storage performance evaluation method of a lithium ion battery anode material, which is characterized by simulating the environmental state of the anode material in the high-temperature storage of a full battery, preparing the lithium-removed anode material by removing lithium by a chemical method, and carrying out equivalent high-temperature storage test on the lithium-removed anode material; the gas production rate is evaluated through the volume change before and after high-temperature storage, and the capacity retention rate is evaluated through the first discharge capacity ratio. The method is simple and convenient to operate and low in cost, sample preparation and high-temperature storage test can be completed in a short period, meanwhile, interference of the cathode material is reduced, and the accuracy of high-temperature storage evaluation of the cathode material is improved.
Description
Technical Field
The invention relates to the field of lithium ion battery materials, in particular to a method for evaluating the storage performance of a lithium ion battery anode material.
Background
The lithium ion battery has the advantages of high platform voltage, high energy density, light weight, small volume, small environmental pollution and the like, becomes a current research hotspot, and is widely applied to the fields of 3C intelligent terminals, energy storage, electric automobiles and the like. In a high-temperature use state of the lithium ion battery, a series of reactions between the anode and cathode materials and the electrolyte can generate gas to cause the phenomena of battery swelling and the like, and the application range of the lithium ion battery is restricted to a certain extent. The gas in the lithium ion battery is mainly generated by chemical reaction between the anode and the cathode and the electrolyte in a high-temperature state. At present, the high-temperature storage characteristics of the lithium ion battery cathode material are mainly evaluated by manufacturing a soft package full battery. The testing method has the advantages of long period and complex process, and is easily influenced by the interference of different lithium ion battery cathode materials used by various manufacturers and other factors, so that the testing result has uncertainty.
Therefore, an evaluation method for rapidly judging the high-temperature storage performance of the lithium ion battery anode material is needed, so that the test efficiency is improved, and meanwhile, the evaluation cost is reduced.
In the article of 'research on new methods for testing high-temperature storage performance of lithium ion battery positive material', Peng et al, proposes to establish a new testing method by using button cells to quickly judge the high-temperature storage performance of the positive material and indicate that the floating charge capacity test of the button cells has a linear relationship with the test results of the high-temperature storage swelling rate and the internal resistance increase rate of the soft package lithium battery. Therefore, the high-temperature storage performance of the cathode material can be evaluated by utilizing the advantages of fast button cell manufacturing, simple process, fast evaluation and the like. However, the method only researches the relation between the specific capacity of the float charge test and the high-temperature storage internal resistance of the full battery, the test result may be influenced by different cathode materials, and the accuracy of the test result still has a space for improvement.
Patent CN108267693B discloses a method for rapidly evaluating the high-temperature storage performance of a lithium battery positive electrode material, which uses a lithium ion button half cell to perform high-temperature floating charge on the positive electrode material, and can estimate the difference of the high-temperature storage performance between different positive electrode materials according to the floating charge capacity test data. However, the rapid evaluation method can only estimate the difference of high-temperature storage performance between different cathode materials, and cannot visually represent the performance change of the cathode material during high-temperature storage.
Disclosure of Invention
In order to solve the technical problems, improve the high-temperature storage performance evaluation efficiency of the lithium ion battery anode material, reduce the evaluation cost and reduce the storage evaluation interference factors, the invention provides a novel high-temperature storage evaluation method of the lithium ion battery anode material.
The solution of the invention is realized by the following steps: simulating the environmental state of the anode material in the full-battery high-temperature storage, preparing the delithiated anode material by chemical delithiation, and performing equivalent high-temperature storage test on the delithiated anode material.
The invention provides a method for evaluating the storage performance of a lithium ion battery anode material, which specifically comprises the following steps:
1. and preparing the delithiated anode material.
And adding a certain amount of oxidant into the anode material, and carrying out chemical reaction to obtain the delithiated anode material.
The positive electrode material mainly includes: LiMPO4，M:Fe/Mn/V；LiMnO4；LiMO2，M:Ni/Co/Mn。
The oxidizing agent comprises: perchlorate, permanganate, hydrogen peroxide, peracetic acid, liquid bromine, and organic oxidants such as nitro tetrafluoroborate, peracetic acid, performic acid, dicumyl peroxide, benzoyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, and the like.
The reaction mass ratio of the cathode material to the oxidant is determined according to a chemical reaction equation.
Further, a delithiated positive electrode material was prepared in a glove box filled with argon gas.
Further, after the anode material is added with the oxidant, the reaction temperature is as follows: t is more than or equal to 20 ℃ and less than or equal to 50 ℃, and the reaction time is as follows: h is more than or equal to 5H and less than or equal to 24H, and the stirring speed is as follows: r is more than or equal to 20R/min and less than or equal to 60R/min. Preferably, T is more than or equal to 20 ℃ and less than or equal to 40 ℃, H is 20-24H, and R is 20-40R/min.
Further, the delithiated anode material after the chemical reaction is cleaned by an organic solvent and dried in vacuum. The organic solvent includes: ethanol, ethylene glycol, isopropanol, acetonitrile, and the like.
2. The delithiated positive electrode material was assembled into a button half cell and tested for first discharge capacity C1.
The lithium-removed positive electrode material is manufactured into a lithium ion button half cell according to a certain method, and the first discharge capacity C1 is measured in a voltage range of 3.0-4.3V and a current range of 0.1C-1.0C.
The method for preparing the button half-cell is as follows: weighing the positive electrode material, the conductive agent and PVDF (polyvinylidene fluoride) according to a certain mass ratio; dissolving PVDF (polyvinylidene fluoride) in a certain amount of NMP (N-methyl pyrrolidone), adding a positive electrode material and a conductive agent, and stirring in a stirrer; uniformly mixing the materials to prepare uniform anode slurry; uniformly coating the prepared positive electrode slurry on an aluminum foil to prepare a pole piece, drying and preparing the pole piece into a positive plate for later use; and assembling the positive plate, a diaphragm, a lithium plate, electrolyte and the like into the CR2016 type button half cell.
3. And measuring the volume change of the delithiated anode material and the electrolyte before and after storage.
Putting a certain mass of the delithiated positive electrode material M1 into an aluminum-plastic film bag, adding a certain mass of electrolyte M2, sealing, and testing the volume V1 by adopting a drainage method; and then placing the aluminum plastic film bag in an environment of 40-80 ℃ for 7-10 days for high-temperature storage test.
And taking out the aluminum-plastic film bag after high-temperature storage, and testing the volume V2 after storage by adopting a drainage method.
4. And assembling the delithiated positive electrode material after high-temperature storage into a button half cell, and testing the capacity C2.
And taking the anode material and the electrolyte which are stored at high temperature out of the aluminum plastic film bag, washing and drying to obtain the delithiated anode material which is stored at high temperature, manufacturing the delithiated anode material into a button half cell, and testing the first discharge capacity C2 of the button half cell in a voltage range of 3.0-4.3V and a current range of 0.1C-1.0C.
5. And evaluating the high-temperature storage performance of the cathode material.
And determining the storage gas production amounts of the delithiated anode material and the electrolyte V2-V1. The smaller the value of V2-V1, the smaller the gas production amount of the anode material during high-temperature storage, and the better the performance.
And determining the storage capacity fading condition C2/C1. The closer the value of C2/C1 is to 1, the higher the capacity retention after high temperature storage, the better the performance.
According to the application field of the cathode material, the values of V2-V1 and the values of C2/C1, the high-temperature storage performance of the cathode material is rapidly and directly evaluated. When the application field of the anode material is sensitive to the change of the gas production rate and relatively does not pay attention to the first discharge capacity or the change of the first discharge capacity is within a certain expected value, the smaller the value of V2-V1 is, the smaller the gas production rate is when the anode material is stored at high temperature is, and the better the performance is; when the application field of the cathode material expects that the first discharge capacity of the cathode material is not attenuated or is extremely attenuated and the gas production rate does not exceed the design value, the closer the value of C2/C1 is to 1, the higher the retention rate of the capacitance after high-temperature storage is, the better the performance is.
In general, the high-temperature storage performance of the cathode material can be rapidly evaluated through intuitive values of V2-V1 and values of C2/C1, and the relevant cathode material can be applied to the most suitable field.
The invention has the beneficial effects that:
1. the method has the advantages that the lithium ion battery delithiated anode material is prepared, the high-temperature storage performance of the lithium ion battery is tested, the change of lithium ions caused by charging and discharging is avoided, the high-temperature storage environment state of the full battery is simulated, the manufacturing process of the full battery is omitted, and the influence of factors such as the type of raw materials, the design of the battery, the process and the like on the storage test of the anode material is effectively eliminated.
2. Through the values of V2-V1 and C2-C1, the change of the gas production rate of the side reaction of the anode material and the electrolyte during high-temperature storage can be quickly and intuitively represented, and the capacity fading condition of the anode material during storage can be determined. The method is simple and convenient to operate and low in cost, sample preparation and high-temperature storage testing can be completed in a short period, meanwhile, interference of the cathode material is reduced, and accuracy of high-temperature storage evaluation of the cathode material is improved.
Drawings
Fig. 1 is a volume histogram before and after high temperature storage of example 1 and comparative examples 1 and 2.
Fig. 2 is a bar graph of the first discharge capacity before and after high-temperature storage in example 1 and comparative example 1.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
delithiated Li0.5Ni1/3Co1/3Mn1/3O2And (4) preparing the material. The main reaction principle of chemical lithium removal by adopting a tetrafluoroborate material is as follows:
LiNi1/3Co1/3Mn1/3O2+0.5NO2BF4→Li0.5Ni1/3Co1/3Mn1/3O2+0.5LiBF4+0.5NO2(molecular weight of each substance of the reaction formula: LiNi1/3Co1/3Mn1/3O296.47, NO2BF4Is 132.82, Li0.5Ni1/3Co1/3Mn1/3O292.997, LiBF494.504, NO2Is 28.02)
The delithiation process was carried out in a glove box filled with argon, and 20g of LiNi was taken1/3Co1/3Mn1/3O2The material was placed in a beaker and 27.54g NO added2BF4Putting the solution into a magneton, setting the rotating speed on a magnetic stirrer to be 40r/min, and stirring for 20 hours to obtain Li0.5Ni1/3Co1/3Mn1/3O2And (3) solution. The solution is rapidly filtered and repeatedly washed by acetonitrile to remove LiBF4After impurities, Li is obtained0.5Ni1/3Co1/3Mn1/3O2The material was dried in a vacuum oven for 8 h.
Taking Li0.5Ni1/3Co1/3Mn1/3O2Weighing quantitative materials according to the mass ratio of positive electrode materials to conductive carbon black to PVDF =95% to 2.5%, dissolving PVDF in quantitative NMP, adding the positive electrode materials and the conductive carbon black, putting the positive electrode materials and the conductive carbon black into a stirrer, stirring for 30min, uniformly mixing the materials, and preparing uniform positive electrode slurry. Uniformly coating the prepared anode slurry on an aluminum foil to prepare a pole piece, and drying in a 120 ℃ oven to prepare the anode piece for later use; and assembling the positive plate, a diaphragm, a lithium plate, electrolyte and the like into the CR2016 type button half cell. Testing of Li Using half-cell button0.5Ni1/3Co1/3Mn1/3O2The first discharge capacity C1 of the material at 0.1C under the voltage range of 3.0-4.3V is 158 mAh/g.
10g of dried Li was taken0.5Ni1/3Co1/3Mn1/3O2The material is placed in an aluminum-plastic bag, and the aluminum-plastic bag is sealed after 5g of electrolyte is added. Placing the aluminum-plastic bag in a beaker filled with a certain volume of water to record the volumeThe volume V1 was 10 ml. Then placing the aluminum-plastic bag after the volume measurement in a 60 ℃ oven for 7 days for storage test, placing the aluminum-plastic bag in a beaker after the test is finished, and recording the volume V2 to be 10.5ml to obtain Li0.5Ni1/3Co1/3Mn1/3O2The gas production rate of the material is 0.5ml after 7 days of storage at 60 ℃, namely the volume change rate is 5%. Storing the tested Li0.5Ni1/3Co1/3Mn1/3O2Taking out the material and the electrolyte, washing with DMC (dimethyl carbonate) solution, drying, assembling the button half cell, testing the half cell under the voltage range of 3.0-4.3V, the first discharge capacity C2 of 0.1C is 155mAh/g, the C2/C1 is 97.48%, and the storage capacity can be 97.48%.
Comparative example 1:
delithiated Li0.5Ni1/3Co1/3Mn1/3O2And (4) preparing the material. The lithium is removed by a chemical method by adopting a tetrafluoroborate and nitrate material, and the main reaction principle is as follows:
LiNi1/3Co1/3Mn1/3O2+0.5NO2BF4→Li0.5Ni1/3Co1/3Mn1/3O2+0.5LiBF4+0.5NO2(molecular weight of each substance of the reaction formula: LiNi1/3Co1/3Mn1/3O296.47, NO2BF4Is 132.82, Li0.5Ni1/3Co1/3Mn1/3O292.997, LiBF494.504, NO2Is 28.02)
The delithiation process was carried out in a glove box filled with argon, and 20g of LiNi was taken1/3Co1/3Mn1/3O2The material was placed in a beaker and 27.54gNO was added2BF4Putting the solution into a magneton, setting the rotating speed on a magnetic stirrer to be 40r/min, and stirring for 20 hours to obtain Li0.5Ni1/3Co1/3Mn1/3O2And (3) solution. The solution is rapidly filtered and repeatedly washed by acetonitrile to remove LiBF4After impurities, Li is obtained0.5Ni1/3Co1/3Mn1/3O2MaterialDrying in a vacuum oven for 8 h.
Taking Li0.5Ni1/3Co1/3Mn1/3O2Weighing quantitative materials according to the mass ratio of positive electrode materials to conductive carbon black to PVDF =95% to 2.5%, dissolving PVDF in quantitative NMP, adding the positive electrode materials and the conductive carbon black, putting the positive electrode materials and the conductive carbon black into a stirrer, stirring for 30min, uniformly mixing the materials, and preparing uniform positive electrode slurry. Uniformly coating the prepared anode slurry on an aluminum foil to prepare a pole piece, and drying in a 120 ℃ oven to prepare the anode piece for later use; and assembling the positive plate, a diaphragm, a lithium plate, electrolyte and the like into the CR2016 type button half cell. Testing of Li Using half-cell button0.5Ni1/3Co1/3Mn1/3O2The first discharge capacity C1 of the material at 0.1C under the voltage range of 3.0-4.3V is 158 mAh/g.
10g of dried Li was taken0.5Ni1/3Co1/3Mn1/3O2The material is placed in an aluminum-plastic film bag, no electrolyte is added, and the aluminum-plastic film bag is sealed. The aluminum-plastic film bag was placed in a beaker containing a volume of water, recording the volume V1 as 10 ml. Then placing the aluminum-plastic film bags with the measured volume in an oven at 60 ℃ for 7 days for storage test, placing the aluminum-plastic film bags in a beaker after the test is finished, and recording the volume V2 to be 10ml, namely Li0.5Ni1/3Co1/3Mn1/3O2The material is stored at 60 ℃ for 7 days without generating gas. Storing the tested Li0.5Ni1/3Co1/3Mn1/3O2The initial discharge capacity C2 of 0.1C of the button half cell assembled by the material is 157.5mAh/g and the first discharge capacity C2/C1 of the button half cell is 99.7 percent under the voltage range of 3.0-4.3V, namely, the gas is not generated in the Li0.5Ni1/3Co1/3Mn1/3O2 material which is not added with electrolyte in storage test, and the capacity is basically kept unchanged.
Comparative example 2:
without addition of Li0.5Ni1/3Co1/3Mn1/3O2Taking 10g of electrolyte, putting the electrolyte into an aluminum-plastic film bag, sealing the aluminum-plastic film bag, putting the aluminum-plastic film bag into a beaker filled with a certain volume of water, and recording the volume V1 to be 10 ml. Then the aluminum plastic film bag after the volume measurement is placed in a 60 ℃ oven for 7 days for storage test,after the test was completed, the aluminum-plastic film bag was placed in a beaker to record a volume V2 of 10ml, i.e., no gassing of the electrolyte itself occurred during 7 days storage at 60 ℃.
The volumes V1 and V2 obtained from the test before and after the high temperature storage of example 1 and comparative example 2 are shown in a bar graph as shown in FIG. 1.
The first discharge capacities C1 and C2 obtained from the test before and after the high temperature storage of example 1 and comparative example 1 were represented by a bar graph as shown in fig. 2.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A method for evaluating the storage performance of a lithium ion battery anode material is characterized by comprising the following steps:
(1) preparing a lithium-removed positive electrode material;
(2) testing the gas production rate of the delithiated anode material and the electrolyte after being stored for a certain time at high temperature;
(3) testing the change of the first discharge capacity of the lithium-removed state positive electrode material before high-temperature storage and after high-temperature storage together with the electrolyte by manufacturing a button half cell;
(4) according to the application field of the anode material, the high-temperature storage performance of the anode material is directly evaluated by combining the gas production rate and the first discharge capacity change.
2. The method for evaluating the storage performance of the lithium ion battery cathode material according to claim 1, wherein the delithiated cathode material is prepared by a chemical method, specifically: the lithium ion battery anode material and an oxidant are subjected to chemical reaction to prepare the delithiated anode material.
3. The method for evaluating the storage performance of the lithium ion battery cathode material according to claim 1, wherein in the step (2), the gas production is tested by a drainage method.
4. The method for evaluating the storage performance of the lithium ion battery cathode material according to claim 3, wherein the specific process of testing the gas production by a drainage method is as follows: putting a certain mass of the delithiated positive electrode material M1 into an aluminum-plastic film bag, adding a certain mass of electrolyte M2, sealing, and testing the volume V1 by adopting a drainage method; then placing the aluminum plastic film bag in an environment of 40-80 ℃ for 7-10 days for high-temperature storage test; taking out the aluminum-plastic film bag after high-temperature storage, and testing the volume V2 after storage by adopting a drainage method; V2-V1 is the gas production rate.
5. The method for evaluating the storage performance of the lithium ion battery positive electrode material according to claim 1, wherein: the specific process of the step (3) is as follows: preparing a lithium-ion button type half cell from the delithiated anode material, and measuring the first discharge capacity C1 of the half cell in a voltage range of 3.0-4.3V and a current range of 0.1C-1.0C; washing and drying the delithiated anode material which is stored with the electrolyte at high temperature, assembling into a button type half cell, and measuring the first discharge capacity C2 of the half cell in the voltage range of 3.0-4.3V and the current range of 0.1C-1.0C; and determining the change of the first discharge capacity of the lithium ion battery anode material before and after high-temperature storage by calculating C2/C1.
6. The method for evaluating the storage performance of the lithium ion battery positive electrode material according to claim 1 or 5, wherein: the button half cell model is CR 2016.
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