CN109119599A - Secondary battery and preparation method thereof - Google Patents

Secondary battery and preparation method thereof Download PDF

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Publication number
CN109119599A
CN109119599A CN201710493733.7A CN201710493733A CN109119599A CN 109119599 A CN109119599 A CN 109119599A CN 201710493733 A CN201710493733 A CN 201710493733A CN 109119599 A CN109119599 A CN 109119599A
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active material
polymer
negative electrode
pole piece
electrode active
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CN109119599B (en
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黄婷
袁毅妮
钟泽
魏奕民
戴璐
高旭光
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Contemporary Amperex Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

Abstract

The application relates to a secondary battery, including positive pole piece, negative pole piece, barrier film and electrolyte, positive pole piece includes positive active material layer, and positive active material layer contains high nickel cathode material, and negative pole piece includes negative active material layer, and negative active material layer contains the polymer, contains the structural unit that formula I is shown in the polymer. For the secondary battery with the positive electrode active material being the high-nickel positive electrode material, the polymer containing the structural unit shown in the formula I is used in the negative electrode active material layer, so that the storage capacity of the secondary battery under high temperature and high SOC can be obviously improved, and the gas generation of a battery core is reduced.

Description

A kind of secondary cell and preparation method thereof
Technical field
This application involves secondary cell fields, specifically, are related to the preparation of a kind of secondary cell and the secondary cell Method.
Background technique
In face of increasingly serious problem of environmental pollution, environmentally protective electric car has been to be concerned by more and more people and pushes away It is high.The popularization and promotion and secondary cell of electric car, the especially rise of lithium-ion-power cell and development are closely bound up.With Traditional lithium cobalt material is that the consumer lithium ion battery (mobile phone with Notebook Battery etc.) of anode is compared, and lithium-ion-power cell needs More preferable using security performance, energy density is higher and the lower technology path of cost, faces these demands, stratiform tertiary cathode Material NCM (Li [NixMnyCoz]O2, wherein x+y+z=1) and it comes into being.Compared with LCO positive electrode, introduced in NCM material Mn and Ni element, Mn element therein does not have chemical activity, but can improve the safety and stability of material, while may be used also Reduce material cost.Ni element can also reduce material cost, and can improve the gram volume of material, and the angle promoted from gram volume is come It says, the higher the better for Ni content.The chemical formula of common nickelic positive electrode is Li [NixCoyBz]O2, wherein B is Mn or Al, x+y + z=1 and x >=0.5.But Ni atom activity itself is high and is easy to the generation mixing of Li atom, easily leads to material itself and was using Continuous taking off in journey, especially when the Ni content in nickelic positive electrode is very high, the taking off of material be fairly obvious and final band Carry out a series of problems, such as battery core storage produces gas, capacity attenuation and D.C. resistance (DC Resistance, DCR) growth.Wherein store Produce important indicator of the gas as lithium ion battery safety performance and life appraisal, be always high-nickel material battery core face one sternly High test.
Inside lithium ion cell includes positive and negative anodes active material, collector, isolation film and electrolyte etc., is one very multiple Miscellaneous reactive systems.Battery core is chemically reacted to unavoidable meeting when long-time is placed, and these reactions will generate gas Body.Wherein the state-of-charge (SOC) of power battery pack is one of the important parameter for characterizing lithium battery group state, accurately estimates SOC It is the guarantee of lithium battery group safety and optimal control charge-discharge energy.Under the conditions of low SOC, when especially storage temperature is lower, These chemical reactions carry out more slow, and battery core produces gas can also ignore substantially.But at high SOC, nickelic positive electrode has Very strong oxidisability, if add high temperature catalysis, electrolyte by by containing nickelic positive electrode just extremely fast oxidation and it is big Amount is generated with CO2Based on gas.The injection of these gases leads to battery core bulging inside battery core, and accumulation to a certain extent afterwards will be hard Shell battery core explosion-proof valve is washed open, to cause battery core failure；Battery core be will lead under extreme case because of deformation short circuit or flammable electrolysis There is the risk smoldered, burn and exploded in liquid leakage.Therefore production gas problem of the high-nickel material battery core at the high SOC of high temperature is not allowed small It looks, it is necessary to be improved using effective method, be avoided because producing the gas bring battery core lost of life and security risk etc. Problem.
In a practical situation, to reduce production gas of the high-nickel material battery core under high temperature and high SOC, positive cladding is generallyd use Or the method for adding positive film for additive, to avoid positive electrode from contacting with the direct of electrolyte, to reach reduction electricity The purpose of core production gas.But anode cladding needs to carry out specially treated to positive electrode, this will greatly increase secondary cell, especially It is the cost of raw material of lithium ion battery, and these clads slowly can be dissolved out and be failed over time.And it forms a film The addition of additive often will increase the impedance of battery core, especially can be to the dynamic performance of battery core, such as multiplying power, high temperature performance Deng causing influence very serious.Therefore, it is badly in need of effectively reducing the secondary cell containing nickelic positive electrode at present, especially Storage of lithium ion battery under the conditions of high temperature high SOC produces gas, and does not increase production cost, while not influencing battery core performance.
In consideration of it, special propose the application.
Summary of the invention
The primary and foremost purpose of the application is to provide a kind of secondary cell.
The second of the application is designed to provide the preparation method of the secondary cell.
To achieve the above object, the technical solution of the application is as follows:
This application provides a kind of secondary cell, including anode pole piece, cathode pole piece, isolation film and electrolyte, it is described just Pole pole piece includes positive electrode active material layer, and the positive electrode active material layer contains nickelic positive electrode；The nickelic positive electrode Chemical formula be LiaNixCoy MzO2, wherein M is selected from least one of Mn, Al, Zr, Ti, V, Mg, Fe, Mo, and 0.95≤a≤ 1.2, x >=0.5, y >=0, z >=0, and x+y+z=1；
The cathode pole piece includes negative electrode active material layer, and polymer is contained in the negative electrode active material layer, described poly- It closes in object containing structural unit shown in Formulas I；
Wherein,
R1Selected from hydrogen, halogen, substituted or unsubstituted alkyl；
M is selected from metal ion, amino, substituted or unsubstituted alkyl, substituted or unsubstituted amido and substitution or does not take One of the alkyl carbonyl in generation；
Substituent group is selected from halogen.
Preferably, there is a clad on the surface of the nickelic positive electrode, the element of the clad be selected from Zr, Ti, Ce, V, At least one of Mg, Al, Fe, Cr, Mo, Zn, B, Si.
Preferably, in the polymer containing structural unit shown in Formula II, formula III, formula IV, Formula V and Formula IV at least one Kind:
Wherein:
M1Selected from Na or K；
R11And R14It is each independently selected from as substituted or unsubstituted C1~C12Alkyl；
R12And R13It is each independently selected from hydrogen or C1~C12Alkyl；
Substituent group is halogen.
Preferably, the polymer is selected from least one of homopolymer, copolymer or blend, the preferably described polymer Monomer be selected from methyl acrylate, ethyl acrylate, propyl acrylate, sodium acrylate, potassium acrylate, acrylamide.
Preferably, the number-average molecular weight of the polymer is 2000~20,000,000.
Preferably, mass percentage of the polymer in negative electrode active material layer is 0.5%~10%, preferably 2%~4%.
Preferably, the negative electrode active material layer also includes negative electrode active material, binder and thickener, preferably described negative The mass percentage of pole active material is 85~98%, and the mass percentage of the binder is 0~5%, the thickening The mass percentage of agent is 0.5%~1.5%.
Preferably, the charge cutoff voltage of the secondary cell is more than or equal to 4.1V.
Present invention also provides the preparation methods of the secondary cell, at least include the following steps:
Step 1: will include the anode sizing agent of the nickelic positive electrode, conductive agent and binder coated on anode collection Body surface face forms positive film layer, obtains the anode pole piece after drying；
Step 2: will include the negative electrode slurry of the polymer, negative electrode active material, binder and thickener coated on negative Pole collection liquid surface forms cathode film layer, obtains the cathode pole piece after drying；
Step 3: being wound after the anode pole piece, isolation film and cathode pole piece are successively stacked or tabletting, obtain naked Battery core is then injected into the electrolyte, the secondary cell is obtained after encapsulation.
Preferably, in step 2, first the polymer is dissolved in the partial solvent for preparing the negative electrode slurry, is obtained Mixture A；Then the negative electrode active material, binder and thickener are added in remaining solvent, obtain mixture B； Mixture A is mixed with mixture B finally, obtains the negative electrode slurry.
The technical solution of the application at least has following beneficial effect:
It is the secondary cell of nickelic positive electrode for positive electrode active materials, the application uses in negative electrode active material layer Polymer containing structural unit shown in Formulas I can be substantially reduced battery core and produce gas, improve secondary cell at the high SOC of high temperature Storage capacity.
Specific embodiment
Combined with specific embodiments below, the application is further described.It should be understood that these embodiments are merely to illustrate the application Rather than limitation scope of the present application.
This application involves a kind of secondary cell, including anode pole piece, cathode pole piece, isolation film and electrolyte, anode pole pieces Including positive electrode active material layer, positive electrode active material layer contains nickelic positive electrode；Cathode pole piece includes negative electrode active material layer, Negative electrode active material layer contains polymer, contains structural unit shown in Formulas I in polymer.
In this application, nickelic positive electrode refer to nickel content (molfraction of the nickel in positive electrode active materials) be greater than or Nickeliferous positive electrode equal to 50%.Specifically, the chemical formula of nickelic positive electrode is LiaNixCo y MzO2, wherein M is selected from At least one of Mn, Al, Zr, Ti, V, Mg, Fe, Mo, 0.95≤a≤1.2, x >=0.5, y >=0, z >=0, and x+y+z=1.
In the structural unit shown in Formulas I, R1Selected from hydrogen, halogen, substituted or unsubstituted alkyl；M be selected from metal ion, One of amino, substituted or unsubstituted alkyl, substituted or unsubstituted amido and substituted or unsubstituted alkyl carbonyl；Replace Base is selected from halogen.
Applicants have found that use contains in cathode when the positive electrode active materials of secondary cell are nickelic positive electrode When the polymer of structural unit shown in Formulas I, it can change under the premise of not increasing battery manufacturing cost and not damaging battery performance It is apt to it and stores the problem of producing gas at the high SOC of high temperature, to avoids because producing the gas bring battery core lost of life and security risk.
Further mechanism study shows that the anode pole piece containing nickelic positive electrode has under conditions of high temperature high SOC There is very strong oxidisability, by electrolyte oxidation and a large amount of CO can be generated2, battery core is caused quickly to produce gas.If in cathode The polymer containing structural unit shown in Formulas I is added, which can be by cyclic ester, ol ester and the carboxylate etc. in electrolyte Compound containing ester group dissolves out on a small quantity, forms the electrolyte leachate containing the polymer, which has the SEI film of cathode Certain corrosiveness, so as to cause the destruction of SEI film and the exposing of fresh graphite, the CO that anode pole piece generates at this time2Meeting exists Exposed graphite surface reacts on cathode pole piece, produces new SEI film, the CO generated so as to cause anode2Largely disappeared Consumption, greatly reduces production gas of the secondary cell containing nickelic positive electrode at the high SOC of high temperature.
The preferred lithium ion battery of secondary cell in the application, the lithium ion battery can be takeup type or stacked lithium from Sub- battery.
Further, in the chemical formula of above-mentioned nickelic positive electrode, M is Mn or Al, a=1, x >=0.5, y > 0, z > 0, and x+y+z=1.I.e. nickelic positive electrode is selected from least one of NCM and NCA.
In embodiments herein, nickelic positive electrode can be selected from Li [Ni0.6Co0.2Mn0.2]O2、Li [Ni0.8Co0.1Mn0.1]O2、Li[Ni0.8Co0.1Al0.1]O2At least one of.
The surface of nickelic positive electrode can also be coated in the application, cladding element be selected from Zr, Ti, Ce, V, Mg, At least one of Al, Fe, Cr, Mo, Zn, B, Si.
Further, at least one containing structural unit shown in Formula II, formula III, formula IV, Formula V and Formula IV in polymer:
Wherein, M1Selected from Na or K；
R11And R14It is each independently selected from as substituted or unsubstituted C1~C12Alkyl；
R12And R13It is each independently selected from hydrogen or C1~C12Alkyl；
Substituent group is halogen.
Further, it is added in ordinary graphite cathode formula involved in the application, contains structure list shown in Formulas I The polymer of member, selected from least one of homopolymer, copolymer or blend.The monomer of polymer be selected from methyl acrylate, Ethyl acrylate, propyl acrylate, sodium acrylate, potassium acrylate, acrylamide.
The method for preparing the application polymer is conventional, such as above-mentioned monomer is added in reactor in proportion, is added Initiator and molecular weight regulator, take water as a solvent, and react 4~8 hours under the conditions of 60~80 DEG C, when number-average molecular weight is Reaction was completed when 2000~20,000,000, obtains the polymer of the application.
Wherein, initiator is selected from ammonium persulfate, and molecular weight regulator is lauryl mercaptan.
Further, the number-average molecular weight of polymer is 2000~20,000,000.When polymer number-average molecular weight is less than It when 2000, is easily dissolved by the electrolyte, the improvement for producing gas to battery core is unobvious.When polymer number-average molecular weight be greater than 20,000, When 000, the poor processability of slurry is not easy to form uniform negative electrode active material layer in negative terminal surface.The number-average molecular weight Lower limit be selected from 2000,5000,10,000,15,000, the upper limit be selected from 20,000,000,10,000,000,1,000,000, 100,000。
Due to polymer is identical by chemical composition and homologous mixture that the degree of polymerization is not equal forms, i.e., by molecular chain length Different high polymer mixing compositions is spent, average molecular weight characterization bulk of molecule is generallyd use.By molecule amount statistical average Referred to as number-average molecular weight, symbol are MN (Number-average Molecular Weight).
As a kind of improvement to the application secondary cell, mass percentage of the polymer in negative electrode active material layer It is 0.5%~10%, i.e., adds the poly- containing structural unit shown in Formulas I of 0.5~10wt% in conventional graphite cathode formula Close object.When the content of the polymer is lower than 1%, ideal effect is not achieved in the improvement result that SOC storage high to battery core produces gas, is higher than When 10%, the energy density of battery core is damaged.It is further preferred that the lower limit of the mass percentage be selected from 0.5%, 1%, 2%, 3%, the upper limit is selected from 6%, 8%, 9%, 10%, most preferably 2%~4%.
Further, negative electrode active material layer further includes negative electrode active material, binder and thickener.
Specifically, negative electrode active material is selected from soft carbon, hard carbon, artificial graphite, natural graphite, silicon, silicon oxide compound, silicon-carbon Compound, lithium titanate can form at least one of the metal of alloy with lithium.Wherein, silicon oxide compound SiOx, 0.5 < x < 2. Silicon-carbon compound is selected from graphite-hard charcoal mixing material, graphite-silicon materials combined material, graphite-hard charcoal-silicon materials combined material.
Specifically, binder is selected from polyvinyl alcohol, polytetrafluoroethylene (PTFE), Kynoar, water system acrylic resin, ethylene- At least one of vinyl acetate co-polymer, butadiene-styrene rubber, Viton and polyurethane.
Specifically, thickener is surfactant, such as sodium carboxymethylcellulose (CMC).
Specifically, in negative electrode active material layer, the mass percentage of negative electrode active material is 85%~98%, bonding The mass percentage of agent is 0~5%, and the mass percentage of thickener is 0.5%~1.5%.
Further, the positive electrode active material layer of the application further includes binder and conductive agent.
Specifically, binder is selected from polyvinyl alcohol, polytetrafluoroethylene (PTFE), Kynoar, sodium carboxymethylcellulose, water system third At least one of olefin(e) acid resin, ethylene-vinyl acetate copolymer, butadiene-styrene rubber, Viton and polyurethane.
Specifically, conductive agent is carbon material, at least one in graphite, carbon black, graphene, carbon nanotube conducting fiber Kind.Common conductive agent includes Ketjen black (ultrafine electricity conductive carbon black, partial size 30-40nm), SP (Super P, little particle conductive carbon Black, partial size is 30-40 μm), S-O (ultra micro fine graphite powders, partial size be 3-4 μm), (bulky grain graphite powder, partial size are 6.5 μ to KS-6 M), acetylene black, VGCF (gas-phase growth of carbon fibre, partial size are 3-20 μm).Available conductive agent further includes metal powder, conduction Whisker, conductive metallic compound, conducting polymer etc..
Specifically, in positive electrode active material layer, the mass percentage of nickelic positive electrode is 80~98%, binder Mass percentage be 1~10%, the mass percentage of conductive agent is 1~10%.
Further, the application is not particularly limited the material of isolation film, be polymeric barrier films, can be selected from polyethylene, One of polypropylene and ethylene-propylene copolymer.
Further, electrolyte includes organic solvent, lithium salts and additive.
Specifically, organic solvent in the conventional organic solvents such as cyclic carbonate, linear carbonates and carboxylate one Kind is several.It specifically can be selected from following organic solvent to be not limited to this: ethylene carbonate, propylene carbonate, dimethyl carbonate, carbon Diethyl phthalate, dipropyl carbonate, methyl ethyl carbonate, methyl formate, Ethyl formate, ethyl propionate, propyl propionate, methyl butyrate, Ethyl acetate.
Specifically, lithium salts is selected from least one of inorganic lithium salt and organic lithium salt.Inorganic lithium salt is selected from lithium hexafluoro phosphate (LiPF6), LiBF4 (LiBF4), hexafluoroarsenate lithium (LiAsF6), lithium perchlorate (LiClO4At least one of).It is organic Lithium salts is selected from di-oxalate lithium borate (LiB (C2O4)2, be abbreviated as LiBOB), double fluorine sulfimide lithiums (LiFSI) and double fluoroforms At least one of alkane sulfimide lithium (LiTFSI).
Specifically, additive is selected from one or more of fluorinated, sulfur-bearing class, the compound of class containing unsaturated double-bond.Tool Body can be selected from following substance and be not limited to this: fluorinated ethylene carbonate, ethylene sulfite, propane sultone, N- methylpyrrole Alkanone, N-METHYLFORMAMIDE, N- methylacetamide, acetonitrile, acrylonitrile, gamma-butyrolacton, methyl sulfide.
Further, since secondary cell can be improved capacity in the case where improving charge cutoff voltage, but for making It is more prominent to produce gas problem, it has to lower after improving charge cutoff voltage with the secondary cell of nickelic positive electrode It is used under charge cutoff voltage.And the scheme in the application is used, use the charge cutoff of the secondary cell of nickelic positive electrode Voltage can reach 4.1V or more.
The application further relates to the preparation method of secondary cell, at least includes the following steps:
Step 1: will include the anode sizing agent of nickelic positive electrode, conductive agent and binder coated on anode collection body surface Face forms positive electrode active material layer after drying, obtains anode pole piece；
Step 2: will include the negative electrode slurry of polymer, negative electrode active material, binder and thickener coated on cathode collection Flow surface forms negative electrode active material layer after drying, obtains cathode pole piece.
Step 3: being wound after anode pole piece, isolation film and cathode pole piece are successively stacked or tabletting, naked electricity is obtained Core is then injected into electrolyte, obtains secondary cell after encapsulation.
As a kind of improvement to this method, in step 2, to guarantee that polymer can be in negative electrode active material layer Even distribution is generally dissolved in the partial solvent for preparing negative electrode slurry in advance, obtains mixture A；Then by the cathode Active material, binder and thickener are added in remaining solvent, obtain mixture B；Finally by mixture A and mixture B Mixing, obtains the negative electrode slurry.Particularly, for water base negative electrode slurry, generally polymer is first dissolved in water, in water Mass percentage in solution is 4%~40%.The aqueous solution containing the polymer is added when stirring negative electrode slurry later Enter, makes mass percentage of the polymer in entire negative electrode slurry Solid content 0.5%~10%.
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.
In embodiment, nickelic ternary material NCM622 (Li [Ni0.6Co0.2Mn0.2]O2)、NCM811(Li [Ni0.8Co0.1Mn0.1]O2)、NCA811(Li[Ni0.8Co0.1Al0.1]O2), cladding Zr NCM811 be commercially available.
Embodiment 1
Anode pole piece preparation
Nickelic positive electrode, conductive agent acetylene black, binder Kynoar (PVDF) are mixed, the weight of three's mixing Than for 95:3:2.Solvent N-methyl pyrilidone is added, obtains anode sizing agent after being mixed evenly.Anode sizing agent is uniform Coated on plus plate current-collecting body aluminium foil, it is cold-pressed after then being dried at 85 DEG C, trimming, cut-parts, slitting, it is true at 85 DEG C later Dry 4h, obtains anode pole piece under empty condition.The specific type of nickelic positive electrode used in it is shown in Table 1.
The preparation of cathode pole piece
By negative electrode active material artificial graphite, conductive agent acetylene black, binder butadiene-styrene rubber, thickener CMC, (carboxymethyl is fine Tie up plain sodium) it is mixed according to weight ratio 95:2:2:1, solvent deionized water is added, after being uniformly mixed, is added containing shown in Formulas I The aqueous solution of the polymer of structural unit is again stirring for uniformly obtaining negative electrode slurry.Negative electrode slurry is coated uniformly on cathode collection On fluid copper foil, after being dried at 80-90 DEG C after coating, it is cold-pressed, trimming, cut-parts, slitting, later in 110 DEG C of vacuum items Dry 4h, obtains cathode pole piece under part.The specific type of polymer containing structural unit shown in Formulas I, it is solid in negative electrode slurry Mass percentage in inclusion is shown in Table 1.
Lithium ion battery preparation
Using the polyethylene film of 12 μ m-thicks as isolation film.Hexafluorophosphoric acid lithium concentration is 1mol/L, electrolyte in electrolyte In organic solvent be made of dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), ethylene carbonate (EC), the mass ratio of three For 5:2:3.
Cathode pole piece, isolation film, anode pole piece are successively stacked, isolation film is among anode pole piece and cathode pole piece, Then it is wound into the rectangular naked battery core for being 130mm with a thickness of 8mm, width 60mm, length.Naked battery core is packed into In Aluminium Foil Packing Bag, the vacuum bakeout 10h at 75 DEG C, injection nonaqueous electrolytic solution, by Vacuum Package, stand for 24 hours, later use 0.1C (160mA) Constant current charging to 4.2V, 0.05C (80mA) is then dropped to 4.2V constant-voltage charge to electric current, then with 0.1C The constant current of (160mA) is discharged to 3.0V, is repeated 2 times charge and discharge, finally extremely with the constant current charging of 0.1C (160mA) 3.8V completes the preparation of lithium ion secondary battery.Battery 1~9 is obtained using aforesaid way.
The preparation process of battery 10 is similar to battery 1, when difference is to prepare cathode pole piece, contains structure list shown in Formulas I The polymer of member is directly to mix with negative electrode active material, conductive agent, binder and thickener, and water is then added, stirs evenly Obtain negative electrode slurry.
Table 1
Comparative example 1
The preparation process of battery 1#~5# is as shown in table 2:
Table 2
Test case
High temperature storage test
3 pieces are taken by every group of the battery in embodiment 1 and comparative example 1, is filled at normal temperature with the constant current of 0.5C multiplying power Electricity to voltage is higher than 4.2V, and electric current is further charged under 4.2V constant voltage lower than 0.025C, 4.2V is at and completely fills State.Full charge pond body before test storage is long-pending and is denoted as V0.The battery of fully charged state is placed in 85 DEG C of baking ovens again, stores 2D After take out, the volume after cooling battery core 1h after the storage of test battery core is simultaneously denoted as Vn。
According to formula: ε=(Vn-V0)/V0, calculate the volume change before and after battery storage.After gained each group battery storage Average external volume change rate it is as shown in table 3.
Cycle performance test
3 pieces are taken by every group of the battery in embodiment 1 and comparative example 1, battery is repeated to charge by following steps And electric discharge, and calculate the discharge capacitance of battery.
Firstly, carrying out first time charging and discharging in 25 DEG C of environment, (i.e. bleeding off theoretical appearance in 2h completely in 0.5C The current value of amount) charging current under first carry out constant-current charge, then carry out constant-voltage charge, until upper limit voltage be 4.2V, so Constant-current discharge is carried out under the discharge current of 0.5C afterwards, until final voltage is 2.8V, the discharge capacity that record recycles for the first time.So The charging and discharging circulation for carrying out 200 times afterwards, records the discharge capacity of the 200th circulation.
According to formula: circulation volume conservation rate=(discharge capacity of the 200th circulation/discharge capacity recycled for the first time) × 100%, calculate the capacity retention ratio before and after circulating battery.Average size conservation rate such as 3 institute of table after gained each group circulating battery Show.
Table 3
Through the test result of battery 1#~4# and battery 1~6 it is found that in 622 system battery core of NCM, pass through past cathode The polymer containing structural unit shown in Formulas I that certain content is added in pole piece, can improve the production gas problem of battery core, and can mention The capacity retention ratio of high battery.
In battery 2, when polymer additional amount is 0.2wt%, battery core is stored and produces gas and circulation volume conservation rate only Having slightly improves, and falls flat.
In battery 3, when polymer additional amount be 0.5wt% when, compared with battery 1#, 4.2V completely fill after battery core 85 The gas production that 2D is stored at DEG C can reduce 14.1%, and the conservation rate of the capacity after 200 circulations can be improved 5.8%.
In battery 1, when polymer additional amount increases to 2wt%, can reach improves the effect for producing gas well.With electricity Pond 1# is compared, and the battery core after 4.2V completely fills stores the gas production of 2D at 85 DEG C and can reduce 29.4%, the capacity after 200 circulations Conservation rate can be improved 7.9%.
In battery 4, when the additional amount of polymer further being increased to 4wt%, additional amount compared to 2wt% is produced Although gas and capacity retention ratio have further improvement, but it is little to improve amplitude.In view of the additional amount of polymer is excessive Can have an adverse effect to energy density, it is not necessary to which addition is more than the content of 4wt%.Especially in battery 5 and battery 6, when When the additional amount of polymer increases to 10 or 15wt%, although the production gas to battery core has further improvement, battery core is recycled The damage of capacity retention ratio is larger.
By comparing battery 1# and battery 2#~3#, it can be seen that NCM 811 and NCA 811 is than 622 battery core capacity of NCM It is bigger, but its storage production gas is even more serious, and circulation volume conservation rate is worse.Thus illustrate that battery core Ni content is higher, store Production gas is more serious, and Capacity fading is also faster, therefore seems more urgent to the improvement of the production gas of NCM811 and NCA 811.
By comparing battery 2# and battery 4#, it can be seen that 811 surface NCM is modified through Zr, and the storage of high SOC produces Gas and Capacity fading all have a greater degree of improvement, but still not up to perfect condition.
By comparing battery 2# and battery 7, it can be seen that be added into the cathode pole piece of 811 system of NCM and contain Formulas I institute After showing the polymer of structural unit, test result is similar to 622 system of NCM.The polymer that 2wt% is added can not drop Under the premise of low battery core capacity, production gas situation of the battery core under high SOC high temperature storage is greatly improved, and can be improved circulation volume Conservation rate.The conclusion is equally applicable to 811 system of NCA (battery 3# and battery 8).
By comparing battery 4# and battery 9, it can be seen that NCM 811 is modified through Zr, and 2wt% is added in cathode pole piece Polymer, can be improved battery core capacity, and battery core storage produces gas and Capacity fading can keep preferable state.
By comparing battery 5#, battery 1# battery 1, it can be seen that be added in anode pole piece containing structure list shown in Formulas I The polymer of member can improve the production gas situation of battery core, also have part improvement to the cycle performance of battery core, but improvement is not so good as to incite somebody to action Polymer is obvious for cathode pole piece, therefore is not recommended to use.
By comparing battery 10 and battery 1, it can be seen that the battery core capacity of the two and the production gas situation for improving battery core are basic Quite, but the cycle performance of battery core can be reduced.The reason is that polymer is directly mixed with the raw material of negative electrode slurry, can lead It causes its dispersibility in negative electrode slurry poor, therefore preferably polymer is first dissolved in water, negative electrode active material is then added The stirrings such as material form negative electrode slurry.
By comparing battery 11, battery 1 and battery 1#, it can be seen that the battery core capacity of three is substantially suitable, but battery 11 Cycle performance about the production gas situation and battery core that improve battery core is suitable with battery 1#.The reason is that the molecular weight mistake of polymer It is small, it is easy to be dissolved by the electrolyte, the improvement result for producing gas and cycle performance to battery core is unobvious.
By comparing battery 12, battery 1 and battery 1#, it can be seen that battery 12 is about the production gas situation and electricity for improving battery core Pond 1 is suitable, but the cycle performance of battery core is poor, even lower than battery 1#.Reason may be that the molecular weight of polymer is excessive, slurry Poor processability, be not easy to form uniform negative electrode active material layer in negative terminal surface, although can improve battery core produce gas, It will lead to cycle performance dramatic decrease.
It is not for limiting claim although the application is disclosed as above with preferred embodiment.Any this field skill Art personnel without departing from the concept of this application, can make several possible variations and modification, therefore the application Protection scope should be subject to the range that claim is defined.

Claims (10)

1. a kind of secondary cell, including anode pole piece, cathode pole piece, isolation film and electrolyte, which is characterized in that
The anode pole piece includes positive electrode active material layer, and the positive electrode active material layer contains nickelic positive electrode；The height The chemical formula of nickel positive electrode is LiaNixCoyMzO2, wherein M is selected from least one of Mn, Al, Zr, Ti, V, Mg, Fe, Mo, 0.95≤a≤1.2, x >=0.5, y >=0, z >=0, and x+y+z=1；
The cathode pole piece includes negative electrode active material layer, and polymer, the polymer are contained in the negative electrode active material layer In contain structural unit shown in Formulas I；
Wherein,
R1Selected from hydrogen, halogen, substituted or unsubstituted alkyl；
M is selected from metal ion, amino, substituted or unsubstituted alkyl, substituted or unsubstituted amido and substituted or unsubstituted One of alkyl carbonyl；
Substituent group is selected from halogen.
2. secondary cell according to claim 1, which is characterized in that there is clad on the surface of the nickelic positive electrode, The element of the clad is selected from least one of Zr, Ti, Ce, V, Mg, Al, Fe, Cr, Mo, Zn, B, Si.
3. secondary cell according to claim 1, which is characterized in that in the polymer containing Formula II, formula III, formula IV, At least one of structural unit shown in Formula V and Formula IV:
Wherein:
M1Selected from Na or K；
R11And R14It is each independently selected from as substituted or unsubstituted C1~C12Alkyl；
R12And R13It is each independently selected from hydrogen or C1~C12Alkyl；
Substituent group is halogen.
4. secondary cell according to claim 1, which is characterized in that the polymer is selected from homopolymer, copolymer or total At least one of mixed object,
It is preferred that the monomer of the polymer is selected from methyl acrylate, ethyl acrylate, propyl acrylate, sodium acrylate, acrylic acid Potassium, acrylamide.
5. secondary cell according to any one of claims 1 to 4, which is characterized in that the equal molecule of the number of the polymer Amount is 2000~20,000,000.
6. secondary cell according to claim 1, which is characterized in that matter of the polymer in negative electrode active material layer Measuring percentage composition is 0.5%~10%, preferably 2%~4%.
7. secondary cell according to claim 1, which is characterized in that the negative electrode active material layer also includes negative electrode active Material, binder and thickener,
It is preferred that the mass percentage of the negative electrode active material is 85~98%, the mass percentage of the binder is 0 ~5%, the mass percentage of the thickener is 0.5%~1.5%.
8. secondary cell according to claim 1, which is characterized in that the charge cutoff voltage of the secondary cell be greater than etc. In 4.1V.
9. a kind of preparation method of any one of claim 1 to 8 secondary cell, which is characterized in that include at least following step It is rapid:
Step 1: will include the anode sizing agent of the nickelic positive electrode, conductive agent and binder coated on anode collection body surface Face forms positive film layer, obtains the anode pole piece after drying；
Step 2: will include the negative electrode slurry of the polymer, negative electrode active material, binder and thickener coated on cathode collection Flow surface forms cathode film layer, obtains the cathode pole piece after drying；
Step 3: being wound after the anode pole piece, isolation film and cathode pole piece are successively stacked or tabletting, naked electricity is obtained Core is then injected into the electrolyte, the secondary cell is obtained after encapsulation.
10. according to the method described in claim 9, it is characterized in that, first the polymer being dissolved in and prepares institute in step 2 It states in the partial solvent of negative electrode slurry, obtains mixture A；Then the negative electrode active material, binder and thickener are added Into remaining solvent, mixture B is obtained；Mixture A is mixed with mixture B finally, obtains the negative electrode slurry.
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