WO2022165754A1 - 一种确定电池的电解液注液质量的方法 - Google Patents

一种确定电池的电解液注液质量的方法 Download PDF

Info

Publication number
WO2022165754A1
WO2022165754A1 PCT/CN2021/075542 CN2021075542W WO2022165754A1 WO 2022165754 A1 WO2022165754 A1 WO 2022165754A1 CN 2021075542 W CN2021075542 W CN 2021075542W WO 2022165754 A1 WO2022165754 A1 WO 2022165754A1
Authority
WO
WIPO (PCT)
Prior art keywords
battery
active material
electrolyte
material layer
electrode active
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2021/075542
Other languages
English (en)
French (fr)
Inventor
闫东阳
王卫东
周新辉
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningde Amperex Technology Ltd
Dongguan Amperex Technology Ltd
Original Assignee
Ningde Amperex Technology Ltd
Dongguan Amperex Technology Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningde Amperex Technology Ltd, Dongguan Amperex Technology Ltd filed Critical Ningde Amperex Technology Ltd
Priority to EP21923770.8A priority Critical patent/EP4207481A4/en
Priority to PCT/CN2021/075542 priority patent/WO2022165754A1/zh
Priority to CN202180001815.XA priority patent/CN113366688B/zh
Priority to US17/702,097 priority patent/US12326390B2/en
Publication of WO2022165754A1 publication Critical patent/WO2022165754A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N15/00—Investigating characteristics of particles; Investigating permeability, pore-volume or surface-area of porous materials
    • G01N15/08—Investigating permeability, pore-volume, or surface area of porous materials
    • G01N15/088—Investigating volume, surface area, size or distribution of pores; Porosimetry
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/60—Arrangements or processes for filling or topping-up with liquids; Arrangements or processes for draining liquids from casings
    • H01M50/609—Arrangements or processes for filling with liquid, e.g. electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/0042—Four or more solvents
    • 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

Definitions

  • the present application relates to the technical field of electrochemistry, and in particular to a method for determining the quality of electrolyte injection of a battery.
  • Lithium-ion batteries have the characteristics of large specific energy, high operating voltage, low self-discharge rate, small size and light weight, and are widely used in fields such as electrical energy storage, portable electronic devices and electric vehicles.
  • Electrolyte is one of the important factors affecting the performance of lithium-ion batteries. Therefore, it is necessary to accurately determine the quality of electrolyte that needs to be injected into lithium-ion batteries during the production of lithium-ion batteries, so as to optimize the performance of lithium-ion batteries.
  • the existing method for determining the quality of electrolyte injection of lithium-ion batteries is usually to inject different amounts of electrolytes into lithium-ion batteries that have not been injected, and then perform various performance test experiments on lithium-ion batteries with different electrolyte contents. Determine the optimal electrolyte injection amount based on the experimental results.
  • the above method usually takes 3 to 6 months, the experiment period is long, the efficiency is low, and at the same time, it needs to consume the preparation materials of the battery, resulting in high research and development costs.
  • the purpose of the present application is to provide a method for determining the electrolyte injection quality of a battery, so as to improve the efficiency and accuracy of determining the battery injection quality.
  • the specific technical solutions are as follows:
  • a first aspect of the present application provides a method for determining the electrolyte injection quality of a battery, the method comprising:
  • V 2 V negative electrode active material layer
  • V represents the apparent volume of the negative electrode active material layer
  • ⁇ represents the expansion percentage of the negative electrode active material layer
  • M El represents the electrolyte injection quality of the battery
  • ⁇ El represents the density of the electrolyte
  • the V is determined by the following formula :
  • V 3 ⁇ [V positive electrode active material layer ⁇ (1-A 1 )+V negative electrode active material layer ⁇ (1-A 2 )]
  • a 1 represents the primary efficiency of the positive electrode active material layer
  • a 2 represents the primary efficiency of the negative electrode active material layer
  • ⁇ represents the chemical consumption coefficient
  • V positive electrode active material layer represents the apparent positive electrode active material layer. volume.
  • the V is determined by the following formula :
  • V 4 m c / ⁇ El
  • m c represents the electrolyte mass consumed by the battery during the injection process.
  • the alpha ranges from 5% to 15%.
  • the beta is determined by the formula:
  • ⁇ X represents the mass difference before and after the battery is formed
  • m 1 represents the electrolyte quality before the battery is internalized.
  • the m c is in the range of 0.05 g to 0.6 g.
  • the electrolyte includes cyclic carbonate compounds, linear ester compounds and nitrile compounds.
  • the mass percentage of the cyclic carbonate compound is 20% to 70%
  • the mass percentage of the linear ester compound is 10% to 40%
  • the mass percentage of the nitrile compound is 1% to 15%.
  • the cyclic carbonate compound includes ethylene carbonate, propylene carbonate, diethyl carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate or propyl methyl carbonate At least one of;
  • the linear ester compounds include propyl propionate, ethyl propionate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, methyl butyrate, ethyl butyrate, At least one of ⁇ -butyrolactone or ⁇ -valerolactone;
  • the nitrile compounds include acetonitrile, succinonitrile, adiponitrile, glutaronitrile, hexanetrinitrile, trans-hexenedionitrile, acetonitrile At least one of glycol bis(propionitrile) ether or hexafluorocyclotriphosphazene.
  • the cyclic carbonate compound includes ethylene carbonate, propylene carbonate and diethyl carbonate
  • the linear ester compound includes propyl propionate and ethyl propionate
  • the The nitrile compound includes acetonitrile, wherein the mass ratio between the ethylene carbonate, the propylene carbonate and the diethyl carbonate is 1:1:1-2, the propyl propionate and the propylene carbonate are in a mass ratio of 1:1:1-2.
  • the mass ratio between the ethyl esters is 1:1-2.
  • the present application provides a method for determining the quality of electrolyte injection of a battery.
  • the quality of electrolyte injection the total volume of the positive electrode active material layer, the negative electrode active material layer and the pores in the separator, and the negative electrode activity are fully considered.
  • the material layer ensures the volume of electrolyte required by the battery cycle, the volume of electrolyte consumed by the battery during the formation process, and the volume of electrolyte consumed by the battery during the injection process. Therefore, the determined electrolyte injection quality is closer to the actual maximum. The best injection quality improves the accuracy in determining the electrolyte injection process.
  • the present application saves the time cost and material cost consumed by the long-cycle experimental process, and improves the determination of battery injection.
  • the efficiency of quality makes the electrochemical performance of the battery better and the research and development cost of the battery lower.
  • 1 is a flowchart of a method for determining the electrolyte injection quality of a battery provided by the application;
  • Fig. 2 is the performance test result of the battery of Example 1 of the application at 25°C;
  • Fig. 3 is the performance test result of the battery of Example 2 of the application at 45°C;
  • Fig. 4 is the performance test result of the battery of Example 3 of the application at 45°C;
  • FIG. 5 is the performance test result of the battery of Comparative Example 1 of the application at 25°C;
  • FIG. 6 is the performance test result of the battery of Comparative Example 2 of the application under the condition of 45°C;
  • Fig. 7 is the performance test result of the battery of Comparative Example 3 of the application at 45°C
  • the amount of electrolyte that should be injected can also be calculated based on the physical consumption of the electrolyte, but this method still has the problem that the calculated injection amount and the actual optimum injection quality of the electrolyte have a large deviation.
  • the present application provides a method for determining the quality of electrolyte injection of a battery, as shown in FIG. 1 , including the following steps:
  • the physical filling of the electrolyte in the battery is considered to ensure that the electrolyte is filled in the pores of the positive electrode active material layer, the negative electrode active material layer and the separator, so that the electrolyte can play the role of The role of transporting lithium ions. If local positions of the positive electrode active material layer, negative electrode active material layer and separator cannot be filled with the electrolyte, the positions not filled with the electrolyte cannot exert capacity, resulting in poor electrolyte infiltration of the battery.
  • the electrolyte will enter the pores of the positive electrode active material layer, the negative electrode active material layer and the separator for physical filling. Therefore, the positive electrode can be determined by determining the porosity of the positive electrode active material layer, the negative electrode active material layer and the separator. The total volume V 1 of the pores in the active material layer, the negative active material layer and the separator is determined to determine the electrolyte quality required to fill the positive active material layer, the negative active material layer and the separator.
  • V 2 V negative electrode active material layer
  • V represents the apparent volume of the negative electrode active material layer
  • ⁇ represents the expansion percentage of the negative electrode active material layer
  • Batteries are generally secondary batteries that can be recharged and discharged, and therefore need to be able to be used normally during their cycle.
  • the negative electrode active material layer of the battery is subject to the intercalation and extraction of lithium ions cyclically, resulting in volume expansion of the negative electrode active material layer.
  • the porosity of the negative active material layer in the later cycle of the battery will increase, resulting in an increase in the physical demand for the electrolyte.
  • this application also considers the consumption of electrolyte caused by the expansion of the negative electrode active material layer in the later cycle of the battery, so as to ensure that the battery will not be unable to fill all the pores of the negative electrode active material layer due to insufficient electrolyte content in the later cycle of the battery. Dead zone loses capacity.
  • the expansion percentage ⁇ of the anode active material layer of the present application can be determined according to the expansion characteristics of different anode active material layers in a cycle period, and the value is usually 5% to 15%.
  • the positive electrode and negative electrode in the battery will undergo a film-forming reaction during the first chemical formation, that is, the surface of the positive electrode and the negative electrode will react with the electrolyte components, forming a complex organic-inorganic mixed composition , block the side reaction of the pole piece, and play the role of protecting the pole piece.
  • the present application considers the chemical consumption of the electrolyte during the formation process of the battery, that is, the volume V 3 consumed by the electrochemical reaction of the electrolyte with the positive active material in the positive electrode and the negative active material in the negative electrode.
  • the electrolyte During the battery injection process, due to the influence of other factors, the electrolyte will be consumed to a certain extent.
  • the above other factors are mainly the loss of the injected electrolyte during the manufacturing process, which is generally determined according to different production lines and different production processes.
  • different production lines can mainly refer to: the production line is equipped with different types of liquid injection equipment, chemical forming equipment, gas pumping equipment, weighing equipment, packaging equipment with different types and different precisions, and the total liquid injection tolerance and liquid injection loss. make an impact.
  • Different production processes mainly refer to the adjustment of temperature, humidity, and vacuum parameters in the liquid injection process, the chemical forming process, the gas extraction process, and the packaging process, which have an impact on the total injection tolerance and injection loss.
  • the present application considers the consumption of the electrolyte due to other factors during the injection process, so that the determined quality of the electrolyte injection is more accurate.
  • M El (V 1 +V 2 +V 3 +V 4 ) ⁇ El .
  • the injection quality of the electrolyte can be determined according to the density of the electrolyte.
  • M El represents the electrolyte injection quality of the battery
  • ⁇ El represents the density of the electrolyte.
  • V 1 can be determined by the following formula:
  • V 1 V positive electrode pores +V negative electrode pores +V separator pores
  • V positive electrode pores represent the total volume of pores in the positive electrode active material layer
  • V negative electrode pores represent the total volume of pores in the negative electrode active material layer
  • V separator pores represent the total volume of pores in the separator film.
  • the V cathode porosity can be determined by the following formula:
  • V positive electrode pores S positive electrode active material layer ⁇ V positive electrode active material layer
  • S positive electrode active material layer represents the porosity of the positive electrode active material layer
  • V positive electrode active material layer represents the apparent volume of the positive electrode active material layer
  • V anode porosity is determined by the following formula:
  • V anode pores S anode active material layer ⁇ V anode active material layer
  • S negative electrode active material layer represents the porosity of the negative electrode active material layer
  • V negative electrode active material layer represents the apparent volume of the negative electrode active material layer
  • V- separator porosity is determined by the following formula:
  • V Separator Pore S Separator ⁇ V Separator
  • S separator represents the porosity of the separator
  • V separator represents the apparent volume of the separator
  • the electrolyte volume V consumed by the battery during the formation process is determined by the following formula :
  • V 3 ⁇ [V positive electrode active material layer ⁇ (1-A 1 )+V negative electrode active material layer ⁇ (1-A 2 )]
  • a 1 represents the primary efficiency of the positive electrode active material layer
  • a 2 represents the primary efficiency of the negative electrode active material layer
  • ⁇ represents the chemical conversion consumption coefficient
  • the present application considers the consumption of the electrolyte after the first charge and discharge process of the positive electrode active material layer and the negative electrode active material layer, which is the loss of battery capacity. Therefore, for the positive electrode active material layer, the first efficiency A 1 of the positive electrode active material layer represents the capacity remaining ratio after the battery is formed. By the expression V positive electrode active material layer ⁇ (1-A 1 ), the positive electrode active material layer can be calculated. loss volume. For the negative electrode active material layer, the first efficiency A 2 of the negative electrode active material layer represents the remaining capacity ratio after the battery is formed. By the expression V negative electrode active material layer ⁇ (1-A 2 ), the loss of the negative electrode active material layer can be calculated volume.
  • the present application considers the chemical conversion consumption coefficient ⁇ , and this value can be determined through chemical conversion consumption experiments of the chemical system.
  • the conversion consumption coefficient is determined by the following formula:
  • ⁇ X represents the mass difference before and after the battery is formed
  • m 1 represents the electrolyte quality before the battery is formed.
  • an excess electrolyte solution with a mass of m 1 can be injected into the battery that has not been filled with electrolyte solution, and the battery is weighed to obtain the first mass m x ;
  • the electrolyte volume V4 consumed by the battery during the injection process can be determined by the following formula:
  • V 4 m c / ⁇ El
  • m c represents the mass of electrolyte consumed by the battery during the injection process.
  • the electrolyte consumption mass m c is 0.05 g to 0.6 g.
  • the electrolyte includes cyclic carbonate compounds, linear ester compounds, and nitrile compounds.
  • the cyclic carbonate compound has better dissociation ability to ions and the wetting ability of the electrolyte
  • the linear ester compound has higher conductivity
  • the nitrile compound can improve the SEI film formation of the positive active material layer and the negative active material layer.
  • the mass percentage of the cyclic carbonate compound is 20% to 70%, and the mass percentage of the linear ester compound is 10% to 40%,
  • the mass percentage content of nitrile compounds is 1% to 15%.
  • the mass percentage of the cyclic carbonate compound within the above range by controlling the mass percentage of the cyclic carbonate compound within the above range, the ion dissociation and wettability of the electrolyte can be improved; by controlling the mass percentage of the linear ester compound within the above range, It can improve the conductivity of the electrolyte, avoid lithium precipitation due to excessive local polarization of the electrode pieces, ensure that the battery has no obvious interface defects after long cycles, and improve battery life; by controlling the mass percentage of nitrile compounds Within the above range, it is possible to maintain the storage requirements of the battery cycle, avoid the problem of repeated consumption of electrolyte caused by the breakage and re-filming of the protective films of the positive active material layer and the negative active material layer, and improve the long-term storage stability of the battery .
  • the present application does not have any special restrictions on cyclic carbonate compounds, linear ester compounds and nitrile compounds, as long as they can meet the requirements of the present application.
  • the electrolyte may also include other compounds, for example, including but not limited to: at least one of carboxylate compounds, ether compounds or other organic solvents .
  • the cyclic carbonate compound includes ethylene carbonate, propylene carbonate, diethyl carbonate, butylene carbonate, dimethyl carbonate, ethyl methyl carbonate or methyl propyl carbonate at least one;
  • Linear esters include propyl propionate, ethyl propionate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, methyl butyrate, ethyl butyrate, gamma-butyrolactone or delta- at least one of valerolactone;
  • Nitrile compounds include at least one of acetonitrile, succinonitrile, adiponitrile, glutaronitrile, hexanetrinitrile, trans-hexenedinitrile, ethylene glycol bis(propionitrile) ether or hexafluorocyclotriphosphazene. kind.
  • the hexanetrinitrile may be 1,3,6-hexanetrinitrile.
  • the cyclic carbonate compounds include ethylene carbonate, propylene carbonate and diethyl carbonate
  • the linear ester compounds include propyl propionate and ethyl propionate
  • the nitrile compounds include acetonitrile.
  • the mass ratio between ethylene carbonate, propylene carbonate and diethyl carbonate is 1:1:1-2
  • the mass ratio between propyl propionate and ethyl propionate is 1:1-2.
  • the electrolyte including the above components and contents can further improve the ion dissociation and wettability and long-term storage stability of the electrolyte.
  • the positive electrode active material layer in the present application is not particularly limited as long as the object of the present application can be achieved.
  • the positive electrode active material layer includes a positive electrode active material, and the positive electrode active material is not particularly limited, and any positive electrode active material known in the art can be used, for example, can include nickel cobalt lithium manganate (811, 622, 523, 111), nickel cobalt At least one of lithium aluminate, lithium iron phosphate, lithium-rich manganese-based material, lithium cobaltate, lithium manganate, lithium iron manganese phosphate, or lithium titanate.
  • the negative electrode active material layer in the present application is not particularly limited as long as the object of the present application can be achieved.
  • the negative electrode active material layer includes a negative electrode active material, and the negative electrode active material is not particularly limited, and any negative electrode active material known in the art may be used.
  • at least one of artificial graphite, natural graphite, mesocarbon microspheres, soft carbon, hard carbon, silicon, silicon carbon, titanium niobium compounds, lithium titanate, and the like may be included.
  • the separator of the present application includes, but is not limited to, at least one selected from polyethylene, polypropylene, polyethylene terephthalate, polyimide, or aramid.
  • the polyethylene includes at least one component selected from the group consisting of high density polyethylene, low density polyethylene, and ultra-high molecular weight polyethylene.
  • polyethylene and polypropylene they have a good effect on preventing short circuits and can improve the stability of lithium-ion batteries through the shutdown effect.
  • the surface of the isolation membrane may further include a porous layer, the porous layer is disposed on at least one surface of the isolation membrane, the porous layer includes inorganic particles and a binder, and the inorganic particles are selected from aluminum oxide (Al 2 O 3 ), silicon oxide (SiO 2 ).
  • the adhesive is selected from polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyethylene pyrrole A combination of one or more of alkanone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene, and polyhexafluoropropylene.
  • the porous layer can improve the heat resistance, oxidation resistance and electrolyte wettability of the separator, and enhance the adhesion between the separator and the positive electrode or negative electrode.
  • a lithium-ion battery can be manufactured by the following process: the positive electrode and the negative electrode are separated and stacked by a separator, and they are rolled, folded, etc., as required, and placed into the case, and the electrolyte is injected into the case and sealed.
  • an overcurrent preventing element, a guide plate, etc. can also be placed in the case as required, so as to prevent pressure rise and overcharge and discharge inside the lithium ion battery.
  • the battery in the present application may be a primary battery, a secondary battery, a fuel cell, a solar cell or a capacitor.
  • a typical battery is a lithium-ion battery, which is a secondary battery.
  • Lithium-ion batteries generally include a negative pole piece, a positive pole piece, a separator and an electrolyte.
  • the preparation process of the electrolyte solution is not particularly limited in the present application, for example, the electrolyte solution can be prepared by the following process: the electrolyte solution is obtained by mixing the raw material components constituting the electrolyte solution in proportion and stirring uniformly.
  • Battery size 4.29mm (thickness) ⁇ 44.14mm (width) ⁇ 83.79mm (length), cut-off voltage: 4.45V, battery capacity: 2719mAh.
  • the positive active material lithium cobaltate, acetylene black, and polyvinylidene fluoride (PVDF) were mixed in a mass ratio of 94:3:3, and then N-methylpyrrolidone (NMP) was added as a solvent to prepare a solid content of 75%. slurry and mix well.
  • the slurry was uniformly coated on one surface of an aluminum foil with a thickness of 12 ⁇ m, dried at 90° C., and then cold-pressed to obtain a positive electrode sheet with a positive active material layer thickness of 100 ⁇ m, and then on the other surface of the positive electrode sheet.
  • the above steps are repeated to obtain a positive electrode sheet coated with a positive electrode active material layer on both sides. Weld the positive pole piece to the tab for later use.
  • the negative active material artificial graphite, acetylene black, styrene-butadiene rubber and sodium carboxymethyl cellulose are mixed in a mass ratio of 96:1:1.5:1.5, and then deionized water is added as a solvent to prepare a slurry with a solid content of 70% , and stir well.
  • the slurry was evenly coated on one surface of a copper foil with a thickness of 8 ⁇ m, dried at 110° C., and after cold pressing, a negative electrode pole piece with a negative electrode active material layer thickness of 150 ⁇ m was obtained on one side coated with a negative electrode active material layer, Then, the above coating steps are repeated on the other surface of the negative electrode pole piece to obtain a negative electrode pole piece coated with a negative electrode active material layer on both sides. Weld the negative pole piece to the tab for use.
  • Alumina and polyacrylate were mixed in a mass ratio of 90:10 and dissolved in deionized water to form a ceramic slurry with a solids content of 50%. Then, the ceramic slurry was uniformly coated on one side of the porous substrate (polyethylene, thickness 7 ⁇ m, average pore size 0.073 ⁇ m, porosity 26%) by gravure coating, and dried to obtain a ceramic coating Bilayer structure with porous substrate.
  • Polyvinylidene fluoride and polyacrylate were mixed in a mass ratio of 96:4 and dissolved in deionized water to form a polymer slurry with a solids content of 50%. Then, the polymer slurry is uniformly coated on the two surfaces of the above-mentioned double-layer structure of the ceramic coating layer and the porous substrate by a gravure coating method, and is subjected to drying treatment to obtain a separator.
  • the electrolyte is injected into the battery according to the determined injection quality ME1 .
  • the mass percentage of the cyclic carbonate compound is 45%
  • the mass percentage of the linear ester compound is 40%
  • the mass percentage of the nitrile compound is 15%.
  • cyclic carbonate compounds include ethylene carbonate, propylene carbonate and diethyl carbonate (mass ratio 1:1:1)
  • linear ester compounds include propyl propionate and ethyl propionate (mass ratio 1:1)
  • the nitrile compound is acetonitrile.
  • the battery was cycled at 25°C by the following methods:
  • Battery size 5.06mm (thickness) ⁇ 56.53mm (width) ⁇ 74.3mm (length), cut-off voltage: 4.43V, battery capacity: 3720mAh.
  • the electrolyte is injected into the battery according to the determined injection quality ME1 .
  • the mass percentage of the cyclic carbonate compound is 68%
  • the mass percentage of the linear ester compound is 30%
  • the mass percentage of the nitrile compound is 2%.
  • cyclic carbonate compounds include ethylene carbonate, propylene carbonate and diethyl carbonate (mass ratio 1:1:2)
  • linear ester compounds include propyl propionate and ethyl propionate (mass ratio 1:2)
  • the nitrile compound is succinonitrile.
  • the battery was cycled at 45°C by the following methods:
  • the battery was discharged at 0.7C to a voltage of 3.0V.
  • the battery size is 3.956mm(thickness) ⁇ 44.74mm(width) ⁇ 101.75mm(length), cut-off voltage: 4.35V, battery capacity: 2946mAh.
  • the electrolyte is injected into the battery according to the determined injection quality ME1 .
  • the mass percentage content of the cyclic carbonate compound is 70%
  • the mass percentage content of the linear ester compound is 15%
  • the mass percentage content of the nitrile compound is 15%.
  • cyclic carbonate compounds include ethylene carbonate, propylene carbonate and diethyl carbonate (mass ratio 1:1:1)
  • linear ester compounds include propyl propionate and ethyl propionate (mass ratio 1:1)
  • the nitrile compound is adiponitrile.
  • the battery was cycled at 45°C by the following methods:
  • the battery size, cut-off voltage, and battery capacity are all the same as in Example 1.
  • the liquids were injected according to the following five injection mass gradients: 4.8g, 4.7g, 4.6g, 4.5g, and 4.4g.
  • Example 2 According to the same cycle test method as in Example 1, the above-mentioned five batteries with liquid injection mass gradient were subjected to a cycle test at a temperature of 25°C, and the test results are shown in FIG. 5 .
  • the battery size, cut-off voltage, and battery capacity are the same as those in Example 2.
  • the liquids were injected according to the following seven injection mass gradients: 5.3g, 5.55g, 5.8g, 5.9g, 6.05g, 6.3g, and 6.4g.
  • Example 2 According to the same cycle test method as in Example 2, the above-mentioned seven batteries with liquid injection mass gradient were subjected to a cycle test at a temperature of 45°C, and the test results are shown in FIG. 6 .
  • the battery size, cut-off voltage, and battery capacity are the same as those in Example 3.
  • the electrolyte solution with the same composition as in Example 3 was used, and the solution was injected according to the following five mass gradients: 4.1 g, 4.2 g, 4.3 g, 4.4 g, and 4.5 g.
  • Example 3 According to the same cycle test method as in Example 3, the above-mentioned five batteries with liquid injection mass gradient were subjected to a cycle test at a temperature of 45° C. The test results are shown in FIG. 7 .
  • Example 1 and Comparative Example 1 combined with Figures 2 and 5 that in the method of determining the optimal injection quality of the electrolyte by the gradient design of the electrolyte in Comparative Example 1, the battery with the best cycle performance at 25°C has the best cyclic performance. It is a group with the electrolyte injection quality of 4.5g, which is very close to the electrolyte injection quality of 4.49g determined according to the liquid injection quality determination method of the present application, and the battery cycle performance results obtained by the test at 25°C are at 1000°C. The capacity retention rates after sub-charge-discharge cycles are the same, indicating that the injection quality determined in this application is consistent with the actual optimum injection quality, and the accuracy is high.
  • Example 2 and Comparative Example 2 combined with Fig. 3 and Fig. 6 that in the method of determining the optimal injection quality of the electrolyte through the gradient design of the electrolyte in Comparative Example 2, the battery with the best cycle performance at 45°C has the best cyclic performance. It is a group with an electrolyte injection quality of 6.05g, which is very close to the electrolyte injection quality of 6.00g determined according to the method for determining the injection quality of the present application, and the battery cycle performance results obtained by the test at 45°C are at 800°C. The capacity retention rates after sub-charge-discharge cycles are the same, indicating that the injection quality determined in this application is consistent with the actual optimum injection quality, and the accuracy is high.
  • Example 3 and Comparative Example 3 combined with Fig. 4 and Fig. 7 that in the method of determining the optimal injection quality of the electrolyte through the gradient design of the electrolyte in Comparative Example 3, the battery with the best cycle performance at 45°C has the best cyclic performance. It is a group with an electrolyte injection mass of 4.3g, which is very close to the electrolyte injection mass of 4.33g determined according to the liquid injection quality determination method of the present application, and the battery cycle performance results obtained by the test at 45°C are at 800°C.
  • the capacity retention rate after the sub-charge-discharge cycle is relatively large (about 0.6%), indicating that the injection quality determined in this application is in line with the actual optimal injection quality, even better than the electrolyte injection quality determined by the experimental verification method. accurate.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Pathology (AREA)
  • Immunology (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

本申请提供了一种确定电池的电解液注液质量的方法，包括：确定电池的正极活性材料层、负极活性材料层及隔离膜中孔隙的总体积V 1，确定负极活性材料层保证电池循环周期所需要的电解液体积V 2，确定电池在化成过程中消耗的电解液体积V 3，确定电池在注液过程中消耗的电解液体积V 4，确定电池的电解液注液质量：M El＝(V 1+V 2+V 3+V 4)×ρ El。本申请所确定的电池电解液注液质量更贴近实际最佳注液质量，提高了电解液注液过程中的精确程度，使得电池的电化学性能更优，电池的研发成本更低。

Description

一种确定电池的电解液注液质量的方法 技术领域
本申请涉及电化学技术领域，具体涉及一种确定电池的电解液注液质量的方法。
背景技术
锂离子电池具有比能量大、工作电压高、自放电率低、体积小、重量轻等特点，广泛应用于电能储存、便携式电子设备和电动汽车等领域。
电解液是影响锂离子电池性能的重要因素之一，因此需要在生产锂离子电池的过程中精确确定锂离子电池需要注入的电解液质量，从而使得锂离子电池的性能达到最优。现有的锂离子电池电解液注液质量确定方法通常是对还未注液的锂离子电池注入不同量的电解液，再对具有不同电解液含量的锂离子电池进行各项性能的测试实验，基于实验结果确定最佳的电解液注入量。但是上述方法通常需要3～6个月的时间，实验周期长、效率低，同时需要耗费电池的制备材料，导致研发成本大。
发明内容
本申请的目的在于提供一种确定电池的电解液注液质量的方法，以提高确定电池注液质量的效率及精确程度。具体技术方案如下：
本申请的第一方面提供了一种确定电池的电解液注液质量的方法，所述方法包括：
确定所述电池的正极活性材料层、负极活性材料层及隔离膜中孔隙的总体积V 1；
确定所述负极活性材料层保证所述电池循环周期所需要的电解液体积V 2，其中：
V 2＝V 负极活性材料层×α
式中，V 负极活性材料层表示所述负极活性材料层的表观体积，α表示所述负极活性材料层的膨胀百分比；
确定所述电池在化成过程中消耗的电解液体积V 3；
确定所述电池在注液过程中消耗的电解液体积V 4；
确定所述电池的电解液注液质量：M El＝(V 1+V 2+V 3+V 4)×ρ El
式中，M El表示所述电池的电解液注液质量，ρ El表示所述电解液的密度。
在本申请的一种实施方案中，所述V 3通过下式确定：
V 3＝β×[V 正极活性材料层×(1-A 1)+V 负极活性材料层×(1-A 2)]
式中，A 1表示所述正极活性材料层的首次效率，A 2表示所述负极活性材料层的首次效 率，β表示化成消耗系数，V 正极活性材料层表示所述正极活性材料层的表观体积。
在本申请的一种实施方案中，所述V 4通过下式确定：
V 4＝m c/ρ El
式中，m c表示所述电池在注液过程中消耗的电解液质量。
在本申请的一种实施方案中，所述α的范围为5％至15％。
在本申请的一种实施方案中，所述β通过下式确定：
Figure PCTCN2021075542-appb-000001
式中，ΔX表示所述电池化成前后的质量差，m 1表示所述电池内化成前的电解液质量。
在本申请的一种实施方案中，所述m c的范围为0.05g至0.6g。
在本申请的一种实施方案中，所述电解液包括环状碳酸酯化合物、线性酯类化合物和腈类化合物。在本申请的一种实施方案中，基于所述电解液的总质量，所述环状碳酸酯化合物的质量百分含量为20％至70％，所述线性酯类化合物的质量百分含量为10％至40％，所述腈类化合物的质量百分含量为1％至15％。
在本申请的一种实施方案中，所述环状碳酸酯化合物包括碳酸乙烯酯、碳酸丙烯酯、碳酸二乙酯、碳酸丁烯酯、碳酸二甲酯、碳酸甲乙酯或碳酸甲丙酯中的至少一种；所述线性酯类化合物包括丙酸丙酯、丙酸乙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丁酸甲酯、丁酸乙酯、γ-丁内酯或δ－戊内酯中的至少一种；所述腈类化合物包括乙腈、丁二腈、己二腈、戊二腈、己烷三腈、反式己烯二腈、乙二醇双(丙腈)醚或六氟环三磷腈中的至少一种。
在本申请的一种实施方案中，所述环状碳酸酯化合物包括碳酸乙烯酯、碳酸丙烯酯和碳酸二乙酯，所述线性酯类化合物包括丙酸丙酯和丙酸乙酯，所述腈类化合物包括乙腈，其中，所述碳酸乙烯酯、所述碳酸丙烯酯和所述碳酸二乙酯之间的质量比为1∶1∶1～2，所述丙酸丙酯和所述丙酸乙酯之间的质量比为1∶1～2。
本申请提供了一种确定电池的电解液注液质量的方法，在确定电解液注液质量时，充分考虑了正极活性材料层、负极活性材料层及隔离膜中的孔隙的总体积、负极活性材料层保证电池循环周期所需要的电解液体积、电池在化成过程中消耗的电解液体积、以及电池在注液过程中消耗的电解液体积，因此所确定的电解液注液质量更贴近实际最佳注液质量，提高了在确定电解液注液过程中的精确程度。并且，本申请相较于基于注入不同含量电解液后对电池进行性能测试以确定最佳注液质量的方法，省去了长周期实验过程消耗的时间 成本和物料成本，提高了确定电池注液质量的效率，使得电池的电化学性能更优，电池的研发成本更低。
附图说明
为了更清楚地说明本申请和现有技术的技术方案，下面对实施例和现有技术中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本申请的一些实施例。
图1为本申请提供的一种确定电池的电解液注液质量的方法的流程图；
图2为本申请实施例1电池在25℃条件下的性能测试结果；
图3为本申请实施例2电池在45℃条件下的性能测试结果；
图4为本申请实施例3电池在45℃条件下的性能测试结果；
图5为本申请对比例1电池在25℃条件下的性能测试结果；
图6为本申请对比例2电池在45℃条件下的性能测试结果；
图7为本申请对比例3电池在45℃条件下的性能测试结果
具体实施方式
为使本申请的目的、技术方案、及优点更加清楚明白，以下参照附图和实施例，对本申请进一步详细说明。显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。
在一种实施方案中，还可以基于电解液物理消耗量计算应该注入的电解液量，但是这种方法仍存在计算的注入量与电解液实际最佳注液质量偏差大的问题。有鉴于此，本申请提供了一种确定电池的电解液注液质量的方法，如图1所示，包括以下步骤：
S1，确定电池的正极活性材料层、负极活性材料层及隔离膜中孔隙的总体积V 1。
本申请在确定电解液注液质量时，考虑了电解液在电池内部中的物理填充，保证电解液在正极活性材料层、负极活性材料层及隔离膜的孔隙中填满，使电解液起到传输锂离子的作用。如果上述正极活性材料层、负极活性材料层及隔离膜的局部位置不能被电解液填充，则未被电解液填充的位置无法发挥容量作用，导致电池的电解液浸润不良。
通常而言，电解液会进入正极活性材料层、负极活性材料层及隔离膜的孔隙中进行物理填充，因此可以通过确定正极活性材料层、负极活性材料层及隔离膜的孔隙率，从而确定正极活性材料层、负极活性材料层及隔离膜中孔隙的总体积V 1，进而确定填充正极活性材料层、负极活性材料层及隔离膜所需的电解液质量。
S2，确定负极活性材料层保证电池循环周期所需要的电解液体积V 2。其中：
V 2＝V 负极活性材料层×α
式中，V 负极活性材料层表示负极活性材料层的表观体积，α表示负极活性材料层的膨胀百分比。
电池通常为可充放电循环的二次电池，因此需要能够在其循环周期中正常使用。在电池的循环周期中，电池的负极活性材料层由于受到锂离子循环往复的嵌入和脱出，导致负极活性材料层体积膨胀。不同于电池的负极活性材料层制造初期的孔隙率，负极活性材料层在循环后期的孔隙率会增大，导致对电解液的物理需求增大。因此本申请还考虑了电池循环后期，因负极活性材料层膨胀而引起的电解液的消耗，保证电池在循环后期不会因电解液含量不足而无法填满负极活性材料层的所有孔隙，造成局部死区损失容量。本申请的负极活性材料层的膨胀百分比α可以根据不同负极活性材料层在循环周期中的膨胀特性确定，该数值通常为5％至15％。
S3，确定电池在化成过程中消耗的电解液体积V 3。
电池中的正极极片和负极极片在首次化成过程中会发生成膜反应，即，会在正极极片和负极极片的表面与电解液组分反应，形成的复杂的有机-无机混合成分，阻挡极片发生副反应，起到保护极片的作用。本申请考虑了电池在化成过程中对电解液的化学消耗，即电解液与正极极片中的正极活性材料、负极极片中的负极活性材料发生电化学反应而消耗的体积V 3。
S4，确定电池在注液过程中消耗的电解液体积V 4。
对电池注液过程中，由于受到其他因素的影响，电解液会出现一定消耗。上述其他因素主要为工艺制造过程对注入电解液的损失，一般根据不同的产线和不同的生产工艺来确定。本申请中，不同的产线主要可以指：产线上配备不同型号不同精度的注液设备、化成设备、抽气设备、称重设备、封装设备，对总的注液公差和注液损失量产生影响。不同的生产工艺主要指：注液工序、化成工序、抽气工序、封装工序等工序的温度、湿度、真空度参数调整，对总的注液公差和注液损失量产生影响。本申请考虑了注液过程中因受到其他因素而对电解液的消耗，从而所确定的电解液注液质量更加精确。
S5，确定电池的电解液注液质量：M El＝(V 1+V 2+V 3+V 4)×ρ El。
本申请中，在确定上述V 1、V 2、V 3、V 4后，即可根据电解液的密度确定电解液的注液质量。式中，M El表示电池的电解液注液质量，ρ El表示电解液的密度。
需要说明的是，本申请对上述步骤S1至S4的先后顺序没有特别限制，只要能够通过 上述步骤S1、S2、S3、S4分别确定出V 1、V 2、V 3、V 4即可。
在本申请的一种实施方案中，可以通过下式确定V 1：
V 1＝V 正极孔隙+V 负极孔隙+V 隔离膜孔隙
式中，V 正极孔隙表示正极活性材料层中孔隙的总体积；V 负极孔隙表示负极活性材料层中孔隙的总体积；V 隔离膜孔隙表示隔离膜中孔隙的总体积。
在本申请的一种实施方案中，可以通过下式确定V 正极孔隙：
V 正极孔隙＝S 正极活性材料层×V 正极活性材料层
式中，S 正极活性材料层表示正极活性材料层的孔隙率，V 正极活性材料层表示正极活性材料层的表观体积。
通过下式确定V 负极孔隙：
V 负极孔隙＝S 负极活性材料层×V 负极活性材料层
式中，S 负极活性材料层表示负极活性材料层的孔隙率，V 负极活性材料层表示负极活性材料层的表观体积。
通过下式确定V 隔离膜孔隙：
V 隔离膜孔隙＝S 隔离膜×V 隔离膜
式中，S 隔离膜表示隔离膜的孔隙率，V 隔离膜表示隔离膜的表观体积。
在本申请的一种实施方案中，电池在化成过程中消耗的电解液体积V 3通过下式确定：
V 3＝β×[V 正极活性材料层×(1-A 1)+V 负极活性材料层×(1-A 2)]
式中，A 1表示正极活性材料层的首次效率，A 2表示负极活性材料层的首次效率，β表示化成消耗系数。
本申请考虑了正极活性材料层和负极活性材料层在首次充放电过程后，对电解液产生的消耗，该消耗即为电池容量的损失。因此，对于正极活性材料层，正极活性材料层的首次效率A 1代表了电池化成后的容量剩余比例，通过表达式V 正极活性材料层×(1-A 1)，便可以计算正极活性材料层的损失体积。对于负极活性材料层，负极活性材料层的首次效率A 2代表了电池化成后的容量剩余比例，通过表达式V 负极活性材料层×(1-A 2)，便可以计算负极活性材料层的损失体积。但是，由于正极活性材料层或负极活性材料层的首次效率损失，并非都由活性材料的表面积或体积的损失带来，还包含电极活性材料本身表面成分变化及相变化带来的容量损失。基于此，为了校正该部分的偏差，本申请考虑了化成消耗系数β，该数值可以通过化学体系的化成消耗实验确定。
在本申请的一种实施方案中，化成消耗系数通过下式确定：
Figure PCTCN2021075542-appb-000002
式中，ΔX表示电池化成前后的质量差，m 1表示电池内化成前的电解液质量。
在进行化学体系的化成消耗实验时，可以向未加注过电解液的电池注入质量为m 1的过量电解液，对电池称量，得到第一质量m x；
对注液后的电池进行化成工序，化成后抽出电池内产生的气体，再次对电池称量，得到第二质量m y；
计算ΔX＝m x-m y，即可得到β。
在本申请的一种实施方案中，电池在注液过程中消耗的电解液体积V 4可以通过下式确定：
V 4＝m c/ρ El
式中，m c表示电池在注液过程中消耗的电解液质量。
在本申请的一种实施方案中，电解液消耗质量m c为0.05g至0.6g。
在本申请的一种实施方案中，电解液包括环状碳酸酯化合物、线性酯类化合物和腈类化合物。其中，环状碳酸酯化合物对离子的解离和电解液的浸润能力较好，线性酯类化合物电导率较高，腈类化合物能够提高正极活性材料层和负极活性材料层的SEI成膜性。
在本申请的一种实施方案中，基于电解液的总质量，环状碳酸酯化合物的质量百分含量为20％至70％，线性酯类化合物的质量百分含量为10％至40％，腈类化合物的质量百分含量为1％至15％。
本申请中，通过控制环状碳酸酯化合物的质量百分含量在上述范围内，能够提高电解液的离子解离性和浸润性；通过控制线性酯类化合物的质量百分含量在上述范围内，能够提高电解液的导电性，避免电极极片因局部位置极化过大导致析锂，保证电池在长循环后无明显的界面不良现象，提高电池寿命；通过控制腈类化合物的质量百分含量在上述范围内，能够维持电池循环周期的存储要求，避免因正极活性材料层和负极活性材料层的保护膜破碎和再成膜带来的电解液多次消耗问题，提高电池的长期存储稳定性。
本申请对环状碳酸酯化合物、线性酯类化合物和腈类化合物没有特别限制，只要能满足本申请要求即可。在电解液中除上述环状碳酸酯化合物、线性酯类化合物和腈类化合物以外，还可以包括其他化合物，例如包括但不限于：羧酸酯化合物、醚化合物或其它有机溶剂中的至少一种。
在本申请的一种实施方案中，环状碳酸酯化合物包括碳酸乙烯酯、碳酸丙烯酯、碳酸二乙酯、碳酸丁烯酯、碳酸二甲酯、碳酸甲乙酯或碳酸甲丙酯中的至少一种；
线性酯类化合物包括丙酸丙酯、丙酸乙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丁酸甲酯、丁酸乙酯、γ-丁内酯或δ－戊内酯中的至少一种；
腈类化合物包括乙腈、丁二腈、己二腈、戊二腈、己烷三腈、反式己烯二腈、乙二醇双(丙腈)醚或六氟环三磷腈中的至少一种。在本申请的一种实施方案中，己烷三腈可以是1，3，6-己烷三腈。
在本申请的一种实施方案中，环状碳酸酯化合物包括碳酸乙烯酯、碳酸丙烯酯和碳酸二乙酯，线性酯类化合物包括丙酸丙酯和丙酸乙酯，腈类化合物包括乙腈。其中，碳酸乙烯酯、碳酸丙烯酯和碳酸二乙酯之间的质量比为1∶1∶1～2，丙酸丙酯和丙酸乙酯之间的质量比为1∶1～2。包括上述组分和含量的电解液，能够进一步提高电解液的离子解离性和浸润性以及长期存储稳定性。
本申请中的正极活性材料层没有特别限制，只要能够实现本申请目的即可。例如，正极活性材料层包括正极活性材料，正极活性材料没有特别限制，可以使用本领域公知的任何正极活性材料，例如，可以包括镍钴锰酸锂(811、622、523、111)、镍钴铝酸锂、磷酸铁锂、富锂锰基材料、钴酸锂、锰酸锂、磷酸锰铁锂或钛酸锂中的至少一种。
本申请中的负极活性材料层没有特别限制，只要能够实现本申请目的即可。例如，负极活性材料层包括负极活性材料，负极活性材料没有特别限制，可以使用本领域公知的任何负极活性材料。例如，可以包括人造石墨、天然石墨、中间相碳微球、软碳、硬碳、硅、硅碳、钛铌化合物、钛酸锂等中的至少一种。
本申请的隔离膜包括，但不限于，选自聚乙烯、聚丙烯、聚对苯二甲酸乙二醇酯、聚酰亚胺或芳纶中的至少一种。举例来说，聚乙烯包括选自高密度聚乙烯、低密度聚乙烯和超高分子量聚乙烯中的至少一种组分。尤其是聚乙烯和聚丙烯，它们对防止短路具有良好的作用，并可以通过关断效应改善锂离子电池的稳定性。
隔离膜的表面还可包括多孔层，多孔层设置在隔离膜的至少一个表面上，多孔层包括无机颗粒和粘接剂，无机颗粒选自氧化铝(Al 2O 3)、氧化硅(SiO 2)、氧化镁(MgO)、氧化钛(TiO 2)、二氧化铪(HfO 2)、氧化锡(SnO 2)、二氧化铈(CeO 2)、氧化镍(NiO)、氧化锌(ZnO)、氧化钙(CaO)、氧化锆(ZrO 2)、氧化钇(Y 2O 3)、碳化硅(SiC)、勃姆石、氢氧化铝、氢氧化镁、氢氧化钙和硫酸钡中的一种或多种的组合。粘接剂选自聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、羧甲基纤维素钠、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯和 聚六氟丙烯中的一种或多种的组合。
多孔层可以提升隔离膜的耐热性能、抗氧化性能和电解液浸润性能，增强隔离膜与正极或负极之间的粘接性能。
电池的制备过程为本领域技术人员所熟知的，本申请没有特别的限制。例如锂离子电池可以通过以下过程制造：将正极和负极经由隔离膜隔开堆叠，并根据需要将其卷绕、折叠等操作后放入壳体内，将电解液注入壳体并封口。此外，也可以根据需要将防过电流元件、导板等置于壳体中，从而防止锂离子电池内部的压力上升、过充放电。
本申请对电池没有特别限制，例如可以是一次电池、二次电池、燃料电池、太阳能电池或电容。一种典型的电池就是锂离子电池，其是一种二次电池。锂离子电池一般包含有负极极片、正极极片、隔离膜及电解液。
本申请对电解液的制备过程没有特别限制，例如电解液可以通过以下过程制备：将组成电解液的各原料组分按比例混合并搅拌均匀后，得到电解液。
实施例
以下，举出实施例及对比例来对本申请的实施方式进行更具体地说明。各种的试验及评价按照下述的方法进行。另外，只要无特别说明，“份”、“％”为质量基准。
测试方法和设备：
孔隙率测试：
分别称取一定质量(例如10g)的正极活性材料层、负极活性材料层或隔离膜样品，置于真密度测试仪(型号AccuPycⅡ)中，使测试系统保持密闭，然后通入氮气。真密度测试仪根据样品室和膨胀室中的气体压力，通过波尔定律(PV＝nRT)计算得到样品的孔隙的真实体积，和对应孔隙率数值。
实施例1
电池尺寸：4.29mm(厚)×44.14mm(宽)×83.79mm(长)，截止电压：4.45V，电池容量：2719mAh。
<1-1.正极极片的制备>
将正极活性材料钴酸锂、乙炔黑、聚偏二氟乙烯(PVDF)按质量比94∶3∶3混合，然后加入N-甲基吡咯烷酮(NMP)作为溶剂，调配成固含量为75％的浆料，并搅拌均匀。 将浆料均匀涂覆在厚度为12μm的铝箔的一个表面上，90℃条件下烘干，冷压后得到正极活性材料层厚度为100μm的正极极片，然后在该正极极片的另一个表面上重复以上步骤，得到双面涂覆有正极活性材料层的正极极片。将正极极片焊接极耳后待用。
<1-2.负极极片的制备>
将负极活性材料人造石墨、乙炔黑、丁苯橡胶及羧甲基纤维素钠按质量比96∶1∶1.5∶1.5混合，然后加入去离子水作为溶剂，调配成固含量为70％的浆料，并搅拌均匀。将浆料均匀涂覆在厚度为8μm的铜箔的一个表面上，110℃条件下烘干，冷压后得到负极活性材料层厚度为150μm的单面涂覆负极活性材料层的负极极片，然后在该负极极片的另一个表面上重复以上涂覆步骤，得到双面涂覆有负极活性材料层的负极极片。将负极极片焊接极耳后待用。
<1-3.隔离膜的制备>
将氧化铝与聚丙烯酸酯依照质量比90∶10混合并将其溶入到去离子水中以形成固含量为50％的陶瓷浆料。随后采用微凹涂布法将陶瓷浆料均匀涂布到多孔基材(聚乙烯，厚度7μm，平均孔径为0.073μm，孔隙率为26％)的其中一面上，经过干燥处理以获得陶瓷涂层与多孔基材的双层结构。
将聚偏二氟乙烯与聚丙烯酸酯依照质量比96∶4混合并将其溶入到去离子水中以形成固含量为50％的聚合物浆料。随后采用微凹涂布法将聚合物浆料均匀涂布到上述陶瓷涂层与多孔基材双层结构的两个表面上，经过干燥处理以获得隔离膜。
电解液注液质量的参数及计算结果参见表1-1至表1-5
表1-1
Figure PCTCN2021075542-appb-000003
表1-2
α 负极活性材料层体积(mm 3) V 2(mm 3)
9.2％ 5854.816 538.643
表1-3
Figure PCTCN2021075542-appb-000004
表1-4
电池部件 m c(g) V 4(mm 3)
电池 0.15 130.434
表1-5
V 1+V 2+V 3+V 4(mm 3) ρ El(g/cm 3) M El(g)
3906.132 1.15 4.49
根据所确定的注液质量M El向电池中注入电解液。该电解液中，环状碳酸酯化合物的质量百分含量为45％，线性酯类化合物的质量百分含量为40％，腈类化合物的质量百分含量为15％。其中，环状碳酸酯化合物包括碳酸乙烯酯、碳酸丙烯酯和碳酸二乙酯(质量比1∶1∶1)，线性酯类化合物包括丙酸丙酯和丙酸乙酯(质量比1∶1)，腈类化合物为乙腈。
通过以下方法对电池进行25℃循环测试：
充电模式：
将电池以1.3C恒流充电至4.1V，再恒压充电至电流为1.0C，再以1.0C恒流充电至电压为4.2V，再恒压充电至电流为0.7C，再以0.7C恒流充电至电压为4.3V，再恒压充电至电流为0.4C，再以0.4C恒流充电至电压为4.45V，再恒压充电至电流为0.025C。
放电模式：
在第1次、第49次、第99次、第149次、第199次、第249次、…第999次循环中，将电池以0.2C放电至电压为3.0V；
在第2至第48次、第50至第98次、第100至第148次、第150至第198次、…第 950至第998次、第1000次循环中，将电池以0.5C放电至电压为3.2V。
循环过程中，使用千分尺分别测量第1次、第50次、第100次、第150次、第200次、…第1000次循环测试时，电池充满电的厚度。
电池在25℃条件下的循环测试结果如图2所示。
实施例2
电池尺寸：5.06mm(厚)×56.53mm(宽)×74.3mm(长)，截止电压：4.43V，电池容量：3720mAh。
在制备电池时，<正极极片的制备>、<负极极片的制备>及<隔离膜的制备>的制备工艺均与实施例1相同。
电解液注液质量的参数及计算结果参见表2-1至表2-5
表2-1
Figure PCTCN2021075542-appb-000005
表2-2
α 负极活性材料层体积(mm 3) V 2(mm 3)
11％ 7321.731 805.390
表2-3
Figure PCTCN2021075542-appb-000006
表2-4
电池部件 m c(g) V 4(mm 3)
电池 0.15 130.434
表2-5
V 1+V 2+V 3+V 4(mm 3) ρ El(g/cm 3) M El(g)
5222.394 1.15 6.00
根据所确定的注液质量M El向电池中注入电解液。该电解液中，环状碳酸酯化合物的质量百分含量为68％，线性酯类化合物的质量百分含量为30％，腈类化合物的质量百分含量为2％。其中，环状碳酸酯化合物包括碳酸乙烯酯、碳酸丙烯酯和碳酸二乙酯(质量比1∶1∶2)，线性酯类化合物包括丙酸丙酯和丙酸乙酯(质量比1∶2)，腈类化合物为丁二腈。
通过以下方法对电池进行45℃循环测试：
充电模式：
将电池以1.65C恒流充电至4.1V，再恒压充电至电流为1.5C，再以1.5C恒流充电至电压为4.25V，再恒压充电至电流为1.2C，再以1.2C恒流充电至电压为4.3V，再恒压充电至电流为0.7C，再以0.7C恒流充电至电压为4.43V，再恒压充电至电流为0.025C。
放电模式：
每次循环中，将电池以0.7C放电至电压为3.0V。
循环过程中，使用千分尺分别测量第1次、第50次、第100次、第150次、第200次、…第1000次循环测试时，电池充满电的厚度。
电池在45℃条件下的循环测试结果如图3所示。
实施例3
电池尺寸3.956mm(厚)×44.74mm(宽)×101.75mm(长)，截止电压：4.35V，电池容量：2946mAh。
在制备电池时，<正极极片的制备>、<负极极片的制备>及<隔离膜的制备>的制备工艺均与实施例1相同。
电解液注液质量的参数及计算结果参见表3-1至表3-5
表3-1
Figure PCTCN2021075542-appb-000007
Figure PCTCN2021075542-appb-000008
表3-2
α 负极活性材料层体积(mm 3) V 2(mm 3)
11％ 5108.955 561.985
表3-3
Figure PCTCN2021075542-appb-000009
表3-4
电池部件 m c(g) V 4(mm 3)
电池 0.15 130.434
表3-5
V 1+V 2+V 3+V 4(mm 3) ρ El(g/cm 3) M El(g)
3765.505 1.15 4.33
根据所确定的注液质量M El向电池中注入电解液。该电解液中，环状碳酸酯化合物的质量百分含量为70％，线性酯类化合物的质量百分含量为15％，腈类化合物的质量百分含量为15％。其中，环状碳酸酯化合物包括碳酸乙烯酯、碳酸丙烯酯和碳酸二乙酯(质量比1∶1∶1)，线性酯类化合物包括丙酸丙酯和丙酸乙酯(质量比1∶1)，腈类化合物为己二腈。
通过以下方法对电池进行45℃循环测试：
充电模式：
将电池以1.1C恒流充电至4.05V，再恒压充电至电流为1.0C，再以1.0C恒流充电至 电压为4.1V，再恒压充电至电流为0.7C，再以0.7C恒流充电至电压为4.2V，再恒压充电至电流为0.4C，再以0.4C恒流充电至电压为4.35V，再恒压充电至电流为0.025C。
放电模式：
在第1次、第49次、第99次、第149次、第199次、第249次、…第999次循环中，将电池以0.2C放电至电压为3.0V；
在第2至第48次、第50至第98次、第100至第148次、第150至第198次、…第950至第998次、第1000次循环中，将电池以0.5C放电至电压为3.2V。
循环过程中，使用千分尺分别测量第1次、第50次、第100次、第150次、第200次、…第1000次循环测试时，电池充满电的厚度。
电池在45℃条件下的循环测试结果如图4所示。
对比例1
电池尺寸型号、截止电压、电池容量均与实施例1相同。
使用与实施例1组成相同的电解液，按照以下5个注液质量梯度分别注液：4.8g、4.7g、4.6g、4.5g、4.4g。
按照与实施例1相同的循环测试方法对上述5个注液质量梯度的电池进行25℃温度条件下的循环测试，测试结果如图5所示。
对比例2
电池尺寸型号、截止电压、电池容量均与实施例2相同。
使用与实施例2组成相同的电解液，按照以下7个注液质量梯度分别注液：5.3g、5.55g、5.8g、5.9g、6.05g、6.3g、6.4g。
按照与实施例2相同的循环测试方法对上述7个注液质量梯度的电池进行45℃温度条件下的循环测试，测试结果如图6所示。
对比例3
电池尺寸型号、截止电压、电池容量均与实施例3相同。
使用与实施例3组成相同的电解液，按照以下5个注液质量梯度分别注液：4.1g、4.2g、4.3g、4.4g、4.5g。
按照与实施例3相同的循环测试方法对上述5个注液质量梯度的电池进行45℃温度条件下的循环测试，测试结果如图7所示。
从实施例1和对比例1并结合图2和图5可以看出，对比例1的通过电解液的梯度设 计来确定电解液最佳注液质量的方法中，25℃电池循环性能最好的是电解液注液质量为4.5g的一组，与根据本申请的注液质量确定方法所确定的电解液注液质量4.49g十分接近，且测试得到的25℃度电池循环性能结果、在1000次充放电循环后的容量保持率相同，表明本申请确定的注液质量与实际最佳注液质量相符合，精确度高。
从实施例2和对比例2并结合图3和图6可以看出，对比例2的通过电解液的梯度设计来确定电解液最佳注液质量的方法中，45℃电池循环性能最好的是电解液注液质量为6.05g的一组，与根据本申请的注液质量确定方法所确定的电解液注液质量6.00g十分接近，且测试得到的45℃度电池循环性能结果、在800次充放电循环后的容量保持率相同，表明本申请确定的注液质量与实际最佳注液质量相符合，精确度高。
从实施例3和对比例3并结合图4和图7可以看出，对比例3的通过电解液的梯度设计来确定电解液最佳注液质量的方法中，45℃电池循环性能最好的是电解液注液质量为4.3g的一组，与根据本申请的注液质量确定方法所确定的电解液注液质量4.33g十分接近，且测试得到的45℃度电池循环性能结果、在800次充放电循环后的容量保持率较大(约大0.6％)，表明本申请确定的注液质量与实际最佳注液质量相符合，甚至比通过实验验证方法来确定电解液注液质量更加精确。
从图2至图4还可以看出，随着电池充放电循环次数的增加，电池的膨胀率逐渐升高。
以上所述仅为本申请的较佳实施例，并不用以限制本申请，凡在本申请的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本申请保护的范围之内。

Claims (10)

  1. 一种确定电池的电解液注液质量的方法，其特征在于，所述方法包括：
    确定所述电池的正极活性材料层、负极活性材料层及隔离膜中孔隙的总体积V 1；
    确定所述负极活性材料层保证所述电池循环周期所需要的电解液体积V 2，其中：
    V 2＝V 负极活性材料层×α
    式中，V 负极活性材料层表示所述负极活性材料层的表观体积，α表示所述负极活性材料层的膨胀百分比；
    确定所述电池在化成过程中消耗的电解液体积V 3；
    确定所述电池在注液过程中消耗的电解液体积V 4；
    确定所述电池的电解液注液质量：M El＝(V 1+V 2+V 3+V 4)×ρ El
    式中，M El表示所述电池的电解液注液质量，ρ El表示所述电解液的密度。
  2. 根据权利要求1所述的方法，其中，所述V 3通过下式确定：
    V 3＝β×[V 正极活性材料层×(1-A 1)+V 负极活性材料层×(1-A 2)]
    式中，A 1表示所述正极活性材料层的首次效率，A 2表示所述负极活性材料层的首次效率，β表示化成消耗系数，V 正极活性材料层表示所述正极活性材料层的表观体积。
  3. 根据权利要求1所述的方法，其中，所述V 4通过下式确定：
    V 4＝m c/ρ El
    式中，m c表示所述电池在注液过程中消耗的电解液质量。
  4. 根据权利要求1所述的方法，其中，所述α的范围为5％至15％。
  5. 根据权利要求2所述的方法，其中，所述β通过下式确定：
    Figure PCTCN2021075542-appb-100001
    式中，ΔX表示所述电池化成前后的质量差，m 1表示所述电池内化成前的电解液质量。
  6. 根据权利要求3所述的方法，其中，所述m c的范围为0.05g至0.6g。
  7. 根据权利要求1所述的方法，其中，所述电解液包括环状碳酸酯化合物、线性酯类化合物和腈类化合物。
  8. 根据权利要求7所述的方法，其中，基于所述电解液的总质量，所述环状碳酸酯化合物的质量百分含量为20％至70％，所述线性酯类化合物的质量百分含量为10％至40％，所述腈类化合物的质量百分含量为1％至15％。
  9. 根据权利要求7所述的方法，其中，所述环状碳酸酯化合物包括碳酸乙烯酯、碳酸丙烯酯、碳酸二乙酯、碳酸丁烯酯、碳酸二甲酯、碳酸甲乙酯或碳酸甲丙酯中的至少一种；
    所述线性酯类化合物包括丙酸丙酯、丙酸乙酯、乙酸甲酯、乙酸乙酯、乙酸丙酯、丙酸甲酯、丁酸甲酯、丁酸乙酯、γ-丁内酯或δ－戊内酯中的至少一种；
    所述腈类化合物包括乙腈、丁二腈、己二腈、戊二腈、己烷三腈、反式己烯二腈、乙二醇双(丙腈)醚或六氟环三磷腈中的至少一种。
  10. 根据权利要求8所述的方法，其中，所述环状碳酸酯化合物包括碳酸乙烯酯、碳酸丙烯酯和碳酸二乙酯，所述线性酯类化合物包括丙酸丙酯和丙酸乙酯，所述腈类化合物包括乙腈，其中，所述碳酸乙烯酯、所述碳酸丙烯酯和所述碳酸二乙酯之间的质量比为1∶1∶1～2，所述丙酸丙酯和所述丙酸乙酯之间的质量比为1∶1～2。
PCT/CN2021/075542 2021-02-05 2021-02-05 一种确定电池的电解液注液质量的方法 Ceased WO2022165754A1 (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
EP21923770.8A EP4207481A4 (en) 2021-02-05 2021-02-05 METHOD FOR DETERMINING THE MASS OF ELECTROLYTE INJECTION OF A BATTERY
PCT/CN2021/075542 WO2022165754A1 (zh) 2021-02-05 2021-02-05 一种确定电池的电解液注液质量的方法
CN202180001815.XA CN113366688B (zh) 2021-02-05 2021-02-05 一种确定电池的电解液注液质量的方法
US17/702,097 US12326390B2 (en) 2021-02-05 2022-03-23 Method for determining battery electrolyte injection mass based on electrode swelling, formation consumption, and injection consumption

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2021/075542 WO2022165754A1 (zh) 2021-02-05 2021-02-05 一种确定电池的电解液注液质量的方法

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US17/702,097 Continuation US12326390B2 (en) 2021-02-05 2022-03-23 Method for determining battery electrolyte injection mass based on electrode swelling, formation consumption, and injection consumption

Publications (1)

Publication Number Publication Date
WO2022165754A1 true WO2022165754A1 (zh) 2022-08-11

Family

ID=77523067

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/075542 Ceased WO2022165754A1 (zh) 2021-02-05 2021-02-05 一种确定电池的电解液注液质量的方法

Country Status (4)

Country Link
US (1) US12326390B2 (zh)
EP (1) EP4207481A4 (zh)
CN (1) CN113366688B (zh)
WO (1) WO2022165754A1 (zh)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115939694A (zh) * 2022-08-17 2023-04-07 宁德时代新能源科技股份有限公司 电池单体注液量的确定方法
CN116937088A (zh) * 2023-08-29 2023-10-24 深蓝汽车科技有限公司 一种电池注液量的确定方法及锂离子电池

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114329927B (zh) * 2021-12-14 2025-07-29 惠州锂威新能源科技有限公司 一种电池需求保液量的计算方法
CN115332638B (zh) * 2022-10-14 2023-03-24 宁德新能源科技有限公司 一种电解液、电化学装置和电子装置
JPWO2024147290A1 (zh) * 2023-01-05 2024-07-11
CN116093558A (zh) * 2023-01-31 2023-05-09 湖北亿纬动力有限公司 电池注液量的确定方法
EP4507056A4 (en) * 2023-02-16 2026-04-08 Contemporary Amperex Technology Hong Kong Ltd SECONDARY LITHIUM BATTERY AND ELECTRICAL APPLIANCE
CN116666921B (zh) * 2023-07-31 2024-01-26 宁德时代新能源科技股份有限公司 注液量控制方法、装置、设备、介质及注液系统
CN116908073A (zh) * 2023-08-31 2023-10-20 蜂巢能源科技股份有限公司 一种涂覆隔膜理论孔隙率的计算方法及其应用
CN118670957B (zh) * 2024-08-16 2024-12-17 江苏正力新能电池技术股份有限公司 电池中电解液消耗量的检测方法以及电解液配方的优化方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105787140A (zh) * 2014-12-22 2016-07-20 惠州Tcl金能电池有限公司 确定软包装锂离子电池电解液保有量和注液量的方法
CN108270034A (zh) * 2017-12-29 2018-07-10 苏州润禾化学材料有限公司 一种锂离子电池电解液
CN109802089A (zh) * 2018-12-24 2019-05-24 中国电子科技集团公司第十八研究所 一种超大容量单体电池注液及化成方法
CN110487367A (zh) * 2019-07-18 2019-11-22 合肥国轩高科动力能源有限公司 一种锂离子电池最大安全注液量的评测方法
CN111785910A (zh) * 2020-08-11 2020-10-16 天津市捷威动力工业有限公司 一种确定锂离子电池注液量的方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010001892A1 (ja) * 2008-07-04 2010-01-07 ソニー株式会社 二次電池および電子機器
KR102045478B1 (ko) * 2015-11-30 2019-11-15 주식회사 엘지화학 리튬 이차전지의 전해액 주입량 산출방법
KR102135267B1 (ko) * 2017-06-07 2020-07-17 주식회사 엘지화학 전해액 재주입 가능한 배터리 셀, 배터리 팩, 배터리 팩의 전해액 재주입 시스템 및 배터리 팩의 전해액 재주입 방법
KR102383073B1 (ko) * 2017-07-21 2022-04-04 삼성에스디아이 주식회사 리튬 이차 전지용 전해질 및 이를 포함하는 리튬 이차 전지
CN109920970B (zh) * 2019-03-08 2021-10-08 江西安驰新能源科技有限公司 一种方形铝壳电池的注液时间的计算方法
CN111463398B (zh) 2020-03-16 2022-10-25 宁波维科电池有限公司 一种预估电池100%soc状态下电芯注液量的方法
CN111740168B (zh) * 2020-05-25 2021-06-22 宁波维科电池有限公司 一种电池的制造方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105787140A (zh) * 2014-12-22 2016-07-20 惠州Tcl金能电池有限公司 确定软包装锂离子电池电解液保有量和注液量的方法
CN108270034A (zh) * 2017-12-29 2018-07-10 苏州润禾化学材料有限公司 一种锂离子电池电解液
CN109802089A (zh) * 2018-12-24 2019-05-24 中国电子科技集团公司第十八研究所 一种超大容量单体电池注液及化成方法
CN110487367A (zh) * 2019-07-18 2019-11-22 合肥国轩高科动力能源有限公司 一种锂离子电池最大安全注液量的评测方法
CN111785910A (zh) * 2020-08-11 2020-10-16 天津市捷威动力工业有限公司 一种确定锂离子电池注液量的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4207481A4 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115939694A (zh) * 2022-08-17 2023-04-07 宁德时代新能源科技股份有限公司 电池单体注液量的确定方法
CN116937088A (zh) * 2023-08-29 2023-10-24 深蓝汽车科技有限公司 一种电池注液量的确定方法及锂离子电池

Also Published As

Publication number Publication date
CN113366688A (zh) 2021-09-07
EP4207481A4 (en) 2024-10-02
US20220252498A1 (en) 2022-08-11
US12326390B2 (en) 2025-06-10
CN113366688B (zh) 2022-11-22
EP4207481A1 (en) 2023-07-05

Similar Documents

Publication Publication Date Title
CN113366688B (zh) 一种确定电池的电解液注液质量的方法
CN109873204B (zh) 一种三元锂离子电池电解液及含有该电解液的锂离子电池
CN110931849B (zh) 梯度复合固态电解质及其制备方法和固态锂电池
CA2792747C (en) Lithium secondary battery using ionic liquid
KR101802342B1 (ko) 유기전해액 및 이를 채용한 리튬전지
WO2020052118A1 (zh) 一种锂离子电池电解液及含有该电解液的锂离子电池
EP4181264B1 (en) Secondary battery and device including the same
CN108695547A (zh) 一种有机-无机复合电解质膜及具有该电解质膜的电池
CN110277539A (zh) 正极材料和锂离子电池
CN109994705A (zh) 一种正极极片，其制备方法及电化学装置
CN112467209A (zh) 一种高低温性能兼顾的高电压锂离子电池
AU2015313241A1 (en) Wound electrode group, electrode group, and non-aqueous electrolyte battery
CN112635835B (zh) 高低温兼顾的非水电解液及锂离子电池
CN105070947B (zh) 电解液以及包括该电解液的锂离子电池
WO2024096043A1 (ja) リチウムイオン二次電池用電解液及びリチウムイオン二次電池
WO2025246235A1 (zh) 硅基材料、负极极片、二次电池和装置
CN116670882A (zh) 凝胶聚合物电解质二次电池的制造方法及由此获得的凝胶聚合物电解质二次电池
CN108832180A (zh) 一种锂离子电池电解液及包含该电解液的锂离子电池
CN116315032A (zh) 一种锂离子电池及其制备方法及动力车辆
WO2024183283A1 (zh) 一种二次电池
CN114204038B (zh) 集流体及其应用
CN112825371A (zh) 一种高电压锂离子电池用电解液及包括所述电解液的锂离子电池
CN113906594A (zh) 电解液吸收颗粒、自立片、锂离子二次电池用电极、隔膜及锂离子二次电池
CN108767316A (zh) 一种三元材料体系锂离子电池电解液及锂离子电池
EP4207369A1 (en) Negative electrode plate, electrochemical device, electronic device, and preparation method for negative electrode plate

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21923770

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2021923770

Country of ref document: EP

Effective date: 20230331

NENP Non-entry into the national phase

Ref country code: DE