CN106058315A - Lithium ion battery additive, battery containing additive and preparation method - Google Patents

Lithium ion battery additive, battery containing additive and preparation method Download PDF

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CN106058315A
CN106058315A CN201610633395.8A CN201610633395A CN106058315A CN 106058315 A CN106058315 A CN 106058315A CN 201610633395 A CN201610633395 A CN 201610633395A CN 106058315 A CN106058315 A CN 106058315A
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lithium ion
ion battery
additive
carbonate
solution
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CN106058315B (en
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王珂
史松君
谢岚
王耀辉
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Contemporary Amperex Technology Co Ltd
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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
    • 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
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • 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
    • 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

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Secondary Cells (AREA)

Abstract

The application relates to the field of lithium ion batteries, in particular to a lithium ion battery additive, a battery containing the additive and a preparation method. The additive is a polyvinylpyrrolidone compound and is selected from at least one of compounds shown in a formula I. The electrode material can be effectively soaked by adding the electrolyte into the electrolyte, and the reversible capacity of the battery is improved. Meanwhile, nitrogen elements in the polyvinylpyrrolidone compounds can effectively capture transition metal ions dissolved out of the anode and acid generated by decomposition of the electrolyte, so that the SEI film is prevented from being damaged.

Description

Lithium ion battery additive, the battery containing this additive and preparation method
Technical field
The application relates to field of lithium ion battery, specifically, relates to a kind of lithium ion battery additive, containing this additive Battery and preparation method.
Background technology
Lithium ion battery has high energy density per unit volume, gravimetric specific energy and the good feature of environmental protection, is widely used in hands In the portable 3C electronic equipment such as machine, notebook computer.Along with in recent years electronic product requirement being trended towards less, gentlier, more Thin, in addition to pursuing lower price, pursuing higher energy density becomes the strong driving force improving electronic product.This Outward, various countries strengthen the dynamics of investment to high-power lithium ion battery in recent years, such as electric tool, electric bicycle and automobile Exploitation.As this field is succeeded in developing, the petroleum resources of growing tension can be alleviated, therefore have the highest international economy strategy to anticipate Justice.
Electrolyte is an important component part of lithium ion battery, and its composition directly affects circulation volume and the longevity of battery Life.The electrolyte of composition suitable (relating to selection and the consumption of salt, solvent and additive) can effectively play and promote lithium from The chemical property of sub-battery plus-negative plate material, such as cycle life, capacity holding, high temperature storage, security performance, multiplying power discharging spy Property, the plateau time of electric discharge and the capacity performance etc. of both positive and negative polarity.Generally during lithium ion battery first charge-discharge, electricity Solving some component (solvent or additive) in liquid occurs reduction decomposition and product deposition on the surface of negative material graphite Form solid electrolyte interface film (SEI), or occur oxidation Decomposition and product deposition just to be formed on the surface of positive electrode Interface, pole protecting film.Good and the interface protecting film of densification can alleviate the decomposition of electrolyte, thus reduces the irreversible of battery Capacity also improves its cycle performance.Electrolyte component optimizes, and selecting suitable solvent, lithium salts and additive is to improve interfacial film Effective way.
Exploitation improves the additive of cathode film formation performance, and studies its mechanism of action and film forming component is the most extensively ground Study carefully.Developing more successful organic additive and mainly have 1,2-Asia vinyl carbonate (VC), halogenated carbonate vinyl acetate (is abbreviated as X- EC, X=F, Cl.etc), ethylene sulfite and PS (PS) etc..The effect of these additives is the most preferential In electrolyte solvent generation reduction decomposition, thus suppress the decomposition of electrolyte, and form good SEI at graphite cathode, improve The reversible capacity of electrode and stability.But electrochemical filming can consume active lithium-ion, cause coulombic efficiency first low.
In consideration of it, special, the application is proposed.
Summary of the invention
The primary goal of the invention of the application is to propose a kind of lithium ion battery additive.
Second goal of the invention of the application is to propose the lithium ion battery containing this additive.
3rd goal of the invention of the application is to propose the preparation method of described lithium ion battery.
In order to complete the purpose of the application, the technical scheme of employing is:
The application relates to a kind of lithium ion battery additive, its at least one in compound shown in formula I:
Wherein, described R1、R2And R3It is each independently selected from hydrogen, substituted or unsubstituted C1～C12Alkyl, replacement or do not take The C in generation6～C26Aryl, substituted or unsubstituted C5～C22Heterocyclic base, substituent group is halogen, n=90～3200；Preferably described R1、R2And R3For hydrogen or C1～C8Alkyl.
Preferably, R is worked as1、R2And R3During for hydrogen, described additive is polyvinylpyrrolidone, its structural formula such as Formula II institute Show:
Preferably, the relative molecular mass of described polyvinylpyrrolidone is 10000-360000g/mol.
The application further relates to a kind of lithium ion battery, and it contains positive plate, negative plate, isolating membrane and electrolyte, described Containing lithium salts, organic solvent and additive described herein in electrolyte.
Preferably, described additive and lithium salts be dissolved in organic solvent respectively after, be implanted sequentially in lithium ion battery.
Preferably, described organic solvent contains cyclic carbonate and linear carbonate.Described cyclic carbonate is preferably selected from At least one in ethylene carbonate, Allyl carbonate, gamma-butyrolacton, sulfolane；Described linear carbonate is preferably selected from carbonic acid Dimethyl ester, diethyl carbonate, dipropyl carbonate, Ethyl methyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester, methyl acetate, second At least one in acetoacetic ester, propyl acetate, methyl propionate, ethyl propionate, propyl propionate.
Preferably, described organic solvent possibly together with in carboxylate, sulfone, sulfite, ketone, amine, nitrile, ether, furan at least A kind of.Described carboxylate is selected from methyl butyrate, acrylic acid methyl ester.；Described sulfone is selected from sulfolane, dimethyl sulfoxide；Described sulfite Selected from dimethyl sulfite, diethyl sulfite；Described ketone is selected from N-Methyl pyrrolidone；Described amine is selected from N-methyl first Amide, N-methylacetamide, N,N-dimethylformamide；Described nitrile is selected from acetonitrile, propionitrile, acrylonitrile；Described ether selected from ether, Methyl sulfide；Described furan is selected from oxolane.
Preferably, described lithium salts is selected from LiPF6、LiBF4、LiBOB、LiDFOB、LiAsF6、LiClO4、LiFAP、 LiCF3SO3、Li(FSO2)2N、Li(CF3SO2)2N、Li(C2F5SO2)2At least one in N, is more preferably selected from LiPF6、LiBF4、 Li(FSO2)2At least one in N.
The application further relates to the preparation method of described lithium ion battery, adds in the following manner including by described additive:
Step one, herein described additive is dissolved in the first organic solvent obtains solution A, lithium salts is dissolved in second organic Solvent obtains solution B；
Step 2, solution A is injected in lithium ion battery；And
Step 3, solution B is injected in lithium ion battery.
Preferably, after step 2 terminates, lithium ion battery is stood 6～24h, then carries out step 3.More preferably step After two terminate, lithium ion battery is stood at normal temperatures 6～24h, at 50～70 DEG C, then stands 6～24h, then walk Rapid three.
Preferably, described first organic solvent and the second organic solvent are identical or different, the most identical.
Preferably, the content of described additive is the 0.1%～5% of the gross mass of solution A, and remaining is first organic molten Agent.
Preferably, described lithium salts concentration in solution B is 1.5M～3M.
Preferably, described solution A is 0.5～2:1 with the mass ratio of solution B, more preferably 1:1.
The first organic solvent in described solution A and solution B constitute the electrolyte of lithium ion battery.This electrolyte contains Lithium salts, linear carbonate and cyclic carbonate.The content of the most described cyclic carbonate be the gross mass of electrolyte 10%～ 40%, the content of described linear carbonate is the 40%～70% of the gross mass of electrolyte, described lithium salts in the electrolytic solution dense Degree is 0.3M～1.8M.
What the technical scheme of the application can reach has the beneficial effect that
This application provides a kind of lithium ion battery additive, it is polyvinylpyrrolidone compounds, is added into Electrolyte can effectively infiltrate electrode material, promote the reversible capacity of battery.Meanwhile, polyvinylpyrrolidone compounds The nitrogen element contained can effectively capture transition metal ions and the acid of electrolyte decomposition generation of positive pole dissolution, prevents it from destroying SEI。
In the preferred technical scheme of the application, first pass through the solution A containing polyvinylpyrrolidone compounds and complete To electrode slice and the infiltration of isolating membrane, adding solution B, under the effect of lithium salts, polyvinylpyrrolidone compounds separates out into Film, is coated on electrode slice and isolating membrane surface, provides skeleton for solid electrolyte film (SEI).The distinctive pliability of polymer can To promote the stability of SEI, improve the high temperature cyclic performance of lithium ion battery.
Detailed description of the invention
Below in conjunction with specific embodiment, the application is expanded on further.Should be understood that these embodiments are merely to illustrate the application Rather than restriction scope of the present application.
The application relates to a kind of lithium ion battery additive, and it is polyvinylpyrrolidone compounds, selected from such as Formulas I institute Show at least one in compound:
Wherein, R1、R2And R3It is each independently selected from hydrogen, substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C26Aryl, substituted or unsubstituted C5～C22Heterocyclic base, substituent group is halogen, n=90～3200；Preferably R1、R2And R3For Hydrogen or C1～C8Alkyl.
As a kind of improvement of the application lithium ion battery additive, R1、R2And R3It is each independently selected from hydrogen and C1～C8 Alkyl.
As a kind of improvement of the application lithium ion battery additive, R1、R2And R3For identical substituent group.
In the structure above of the application:
For substituted or unsubstituted C1～C12Alkyl, alkyl can be chain-like alkyl, it is possible to for cycloalkyl, be positioned at cycloalkyl Ring hydrogen can be replaced by alkyl, in described alkyl, the preferred lower limit of carbon number is 1,2,3,4, preferred higher limit is 3,4,5,6,8,10,12.Preferably, the alkyl selecting carbon number to be 1～8, it is further preferred that selecting carbon number is 1 ～the chain-like alkyl of 6, carbon number is the cycloalkyl of 3～8, it is further preferred that the chain selecting carbon number to be 1～3 Alkyl.As the example of alkyl, specifically can enumerate: methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl group, Zhong Ding Base, the tert-butyl group, n-pentyl, isopentyl, neopentyl, hexyl, 2-Methyl pentyl, 3-Methyl pentyl, 1,1,2-trimethyl-the third Base, 3,3 ,-dimethyl-butyl, heptyl, 2-heptyl, 3-heptyl, 2-methylhexyl, 3-methylhexyl, different heptyl, octyl group, nonyl Base, decyl.
For the aryl that carbon number is 6～26, it is preferable that the aryl selecting carbon number to be 6～16, further preferably Ground, the aryl selecting carbon number to be 6～14, it is further preferred that the aryl selecting carbon number to be 6～9.As aryl Example, specifically can enumerate: phenyl, benzyl, xenyl, p-methylphenyl, o-tolyl, a tolyl.
Carbon number is the heterocyclic base of 5～22, is selected from: furyl, thienyl, pyrrole radicals, thiazolyl, imidazole radicals, pyrrole Piperidinyl, pyrazinyl, pyrimidine radicals, pyridazinyl, indyl, quinolyl etc..
As a kind of improvement of the application lithium ion battery additive, work as R1、R2And R3During for hydrogen, described additive is poly- Vinylpyrrolidone, its structural formula is as shown in Formula II:
As a kind of improvement of the application lithium ion battery additive, the relative molecular mass of polyvinylpyrrolidone is 10000-360000g/mol。
As a kind of improvement of the application lithium ion battery additive, the additive of the application is further selected from following compound In at least one:
Wherein n=90～3200, preferably n=100～3000.
The application further relates to a kind of lithium ion battery, and it contains positive plate, negative plate, isolating membrane and electrolyte, described Containing lithium salts, organic solvent and additive described herein in electrolyte.Further, positive plate include plus plate current-collecting body with And the positive electrode active materials being coated on plus plate current-collecting body；Negative plate includes negative current collector and is coated on negative current collector Negative active core-shell material；Isolating membrane is between adjacent positive/negative plate.The upper limit blanking voltage of the lithium ion battery of the application For 3.5V～4.4V.
As a kind of improvement of the application lithium ion battery, positive electrode active materials is selected from cobalt acid lithium, LiMn2O4, nickel cobalt mangaic acid Lithium Li (NixMnyCoz)O2(0<x,y,z<1；X+y+z=1) one or more in；Negative active core-shell material selected from native graphite, One or more in Delanium, soft carbon, hard carbon, lithium titanate, silicon.
As a kind of improvement of the application lithium ion battery, lithium salts is selected from lithium hexafluoro phosphate LiPF6, LiBF4 LiBF4, di-oxalate lithium borate LiB (C2O4)2(being abbreviated as LiBOB), difluorine oxalic acid boracic acid lithium LiBF2(C2O4) (be abbreviated as LiDFOB), hexafluoroarsenate lithium (LiAsF6), lithium perchlorate (LiClO4), three (perfluoro-ethyl) three lithium fluophosphate LiFAP, fluoroform Base Sulfonic Lithium LiCF3SO3, two (trifluoromethane sulfonic acid) lithium methide Li (FSO2)2N, two (trifluoromethane sulfonic acid) imido lithium LiN (CF3SO2)2, two (perfluoro-ethyl sulfonic acid) imido lithium Li (C2F5SO2)2N、Li(C4F9SO2)2N、Li(SO2(CF2)3SO2)2In N At least one, the preferred LiPF of lithium salts6、LiBF4、Li(FSO2)2At least one in N.
As a kind of improvement of the application lithium ion battery, described additive and lithium salts be dissolved in organic solvent respectively after, It is implanted sequentially in lithium ion battery.
The application further relates to the preparation method of described lithium ion battery, adds in the following manner including by described additive:
Step one, herein described additive is dissolved in the first organic solvent obtains solution A, lithium salts is dissolved in second organic Solvent obtains solution B；
Step 2, solution A is injected in lithium ion battery；And
Step 3, solution B is injected in lithium ion battery.
The application it has been investigated that: directly polyvinylpyrrolidone compounds is joined in the organic solvent containing lithium salts The precipitation of polyvinylpyrrolidone compounds can be caused, it is therefore desirable to treat that solution A completes the infiltration to electrode slice and isolating membrane After, add the solution B containing lithium salts.Under the effect of lithium salts, polyvinylpyrrolidone compounds separates out film forming, is coated on electricity Pole piece and isolating membrane surface, provide skeleton for solid electrolyte film (SEI), and the pliability that polymer has can promote SEI's Stability.Meanwhile, the nitrogen element that polyvinylpyrrolidone compounds contains can effectively capture the transition metal of positive pole dissolution The acid that ion and electrolyte decomposition produce, prevents it from destroying SEI, extends the cycle life of battery.
The application it has been investigated that: after step 2 terminates, by lithium ion battery stand 6～24h, then carry out step 3, Polyvinylpyrrolidone compounds can be made to separate out the most abundant.As preferred scheme, first by lithium ion battery often Temperature is lower stands 6～24h, enables electrolyte fully to infiltrate electrode material (mainly physics infiltration), then at 50～70 DEG C Stand 6～24h, it is possible to accelerate the interaction (based on chemical action) of additive and electrode material, beneficially step Acanthopanan trifoliatus (L.) Merr. After entering solution B, polyvinylpyrrolidone compounds forms the film of stable homogeneous at electrode surface.
As a kind of improvement of the application preparation method of lithium ion battery, the first organic solvent and the second organic solvent are identical Or different, the most identical.
As a kind of improvement of the application preparation method of lithium ion battery, in the first organic solvent and the second organic solvent all Containing cyclic carbonate and linear carbonate.Wherein cyclic carbonate is preferably selected from ethylene carbonate (EC), Allyl carbonate (PC), at least one in gamma-butyrolacton, sulfolane；Linear carbonate is preferably selected from dimethyl carbonate, diethyl carbonate (DEC), dipropyl carbonate, Ethyl methyl carbonate (EMC), methyl propyl carbonate, ethyl propyl carbonic acid ester, methyl acetate, ethyl acetate, second At least one in propyl propionate, methyl propionate, ethyl propionate, propyl propionate.
As a kind of improvement of the application preparation method of lithium ion battery, the first organic solvent and/or the second organic solvent In possibly together with at least one in carboxylate, sulfone, sulfite, ketone, amine, nitrile, ether, furan.Wherein carboxylate is selected from butanoic acid first Ester, acrylic acid methyl ester.；Sulfone is selected from sulfolane, dimethyl sulfoxide；Sulfite is selected from dimethyl sulfite, diethyl sulfurous acid Ester；Ketone is selected from N-Methyl pyrrolidone；Amine is selected from N-METHYLFORMAMIDE, N-methylacetamide, N,N-dimethylformamide；Nitrile selects From acetonitrile, propionitrile, acrylonitrile；Ether is selected from ether, methyl sulfide；Furan is selected from oxolane.
As a kind of improvement of the application preparation method of lithium ion battery, the additive level of addition is total matter of solution A The 0.1%～5% of amount, remaining is the first organic solvent.The application it has been investigated that: when content more than 5% time, polyvinyl pyrrole Alkanone compounds ratio in organic solvent is excessive, causes electrolyte system viscosity to become big, simultaneously in both positive and negative polarity surface shape The interfacial film become is blocked up, have impact on the cycle performance of lithium ion battery.But storage performance is improved the most further, this is because high On the one hand the polyvinylpyrrolidone compounds of content can form good interfacial film on both positive and negative polarity surface, reduces positive pole The reactivity on surface, meanwhile, polyvinylpyrrolidone compounds contains lewis base, can neutralize in storing process and produce Sour gas, such as PF5、HF、CO2Deng.When polyvinylpyrrolidone compounds weight/mass percentage composition in the electrolytic solution < When 0.05%, it is impossible to form the protecting film of abundance at electrode slice and isolating membrane surface, to the improvement of the performance of lithium ion battery not Substantially.
As a kind of improvement of the application preparation method of lithium ion battery, the content of the second organic solvent is the total of solution B The 60%～85% of quality, remaining is lithium salts.In addition, also can be containing in addition to herein described additive in solution B Other additive, such as vinylene carbonate, fluorinated ethylene carbonate, sulphuric acid vinylene, 1,3-propane sultone etc..
As a kind of improvement of the application preparation method of lithium ion battery, solution A is 0.5～2 with the mass ratio of solution B: 1, to ensure that the lithium salt in the lithium ion battery of preparation is adjusted within the specific limits with additive concentration, preferably two The mass ratio of person is 1:1.
As a kind of improvement of the application preparation method of lithium ion battery, lithium salts concentration in solution B is 1.5M～3M.
In this application, as additive add polyvinylpyrrolidone compounds almost all electrode slice and every From film surface filming, the first organic solvent in solution A and solution B constitute the electrolyte of lithium ion battery.This electrolyte contains There are lithium salts, linear carbonate and cyclic carbonate, it is also possible to containing other organic solvent and other additive.Preferably cyclic carbonate The content of ester is the 10%～40% of the gross mass of electrolyte, the content of linear carbonate be the gross mass of electrolyte 40%～ 70%, lithium salts concentration in the electrolytic solution is 0.3M～1.8M.
Embodiment 1～6
(1) preparation of the positive plate of lithium ion battery
By positive electrode active materials nickle cobalt lithium manganate (LiNi0.6Co0.2Mn0.2O2), conductive agent Super-P, bonding agent gather inclined fluorine Ethylene (PVDF) during 97.2:1.3:1.5 is dissolved in solvent N-methyl pyrilidone in mass ratio mix homogeneously make anode sizing agent, it After anode sizing agent is uniformly coated on the tow sides of current collector aluminum foil, coating weight is 0.0102g/cm2, subsequently at 85 DEG C Carry out after drying colding pressing, trimming, cut-parts, point bar, under 85 DEG C of vacuum condition, be dried 4h, soldering polar ear afterwards, make lithium ion The positive plate of battery.
(2) preparation of the negative plate of lithium ion battery
By negative active core-shell material Delanium, conductive agent Super-P, thickening agent carboxymethyl cellulose (CMC), bonding agent fourth Benzene rubber (SBR) during 95.4:1.2:1.2:2.2 is dissolved in solvent deionized water in mass ratio mix homogeneously make cathode size, it After cathode size is uniformly coated on the tow sides of copper foil of affluxion body, coating weight is 0.0071g/cm2, subsequently at 85 DEG C Carry out after drying colding pressing, trimming, cut-parts, point bar, under 110 DEG C of vacuum condition, be dried 4h, soldering polar ear afterwards, make lithium ion The negative plate of battery.
(3) preparation of the electrolyte of lithium ion battery
The electrolyte of lithium ion battery is with the LiPF of 1mol/L6For lithium salts, with ethylene carbonate (EC), Ethyl methyl carbonate (EMC) mixture is non-aqueous organic solvent, and wherein the mass ratio of electrolyte solvent part EC:EMC is 30:70.Additionally, lithium from Possibly together with additive in the electrolyte of sub-battery, the title of additive and content in the electrolytic solution are as shown in table 1.In embodiment The K value of the polyvinylpyrrolidone used is 30, purchased from Chemical Reagent Co., Ltd., Sinopharm Group (Chinese).
(4) preparation of lithium ion battery
By the positive plate of lithium ion battery prepared according to previous process, negative plate and isolating membrane, (PE film, containing pottery Coating) through winding process be fabricated to thickness be 5.7mm, width be 16mm, the battery core of a length of 33mm, wherein this battery core leaves Long airbag, in order to observe its aerogenesis.Fluid injection step is divided into following three steps:
Step one, the additive shown in Formula II is dissolved in the first organic solvent obtains solution A, by lithium salts LiPF6It is dissolved in Two organic solvents obtain solution B.Wherein the first organic solvent and the second organic solvent are the mixed solvent of EC and EMC, both Mass ratio is 30:70.In solution A, the weight content of additive is 0.1%～5%, and specific name and content are as shown in table 1.Molten LiPF in liquid B6Content be 2mol/L.
Step 2, solution A is injected in lithium ion battery, stand 12h the most at normal temperatures, then quiet at 50～70 DEG C Put 12h；
Step 3, solution B is injected in lithium ion battery, complete encapsulation.
Lithium ion battery after encapsulation is stood 24h, afterwards by the constant current charge of 0.05C (11mA) to 3.4V, takes It is pre-packaged so that degasification that lower battery the most first carries out vacuum；Again with the constant current charge of 0.05C (11mA) to 4.5V, and After again battery is taken off carry out second time degasification；Then it is discharged to 3V with the constant current of 0.5C (110mA), is repeated 2 times charge and discharge Electricity, finally with the constant current charge of 0.5C (110mA) to 3.85V, completes the preparation of lithium ion battery.
Comparative example 1～3
In comparative example 1, prepare lithium ion battery according to the method for embodiment 1, differ only in electrolyte and do not use Any additive；In comparative example 2～3, the title of additive and content in the electrolytic solution are as shown in table 1, remaining step with Embodiment 1.
Testing example and comparative example prepare high temperature cyclic performance and the high-temperature storage performance of lithium ion battery, detection method As follows:
(1) the high temperature cyclic performance test of lithium ion battery
At 45 DEG C, first with the constant current of 1C, lithium ion battery is charged to 4.2V, further with 4.2V constant voltage Charging to electric current is 0.05C, then with the constant current of 1C, lithium ion battery is discharged to 2.8V, and this is a charge and discharge cycles Process, this discharge capacity is the discharge capacity of the 1st circulation.Lithium ion battery is circulated in a manner described discharge and recharge Test, takes the discharge capacity of the 1000th circulation.
Capability retention (%)=(discharge capacity/1st time of the 100th circulation after 1000 circulations of lithium ion battery The discharge capacity of circulation) × 100%.
(2) the high-temperature storage performance test of lithium ion battery
At 25 DEG C, first with the constant current of 1C, lithium ion battery is charged to 4.2V, further with 4.2V constant voltage Charging to electric current is 0.05C, and then lithium ion battery is placed at 85 DEG C storage 10 days, observes voltage drop.
Volume change (%) after high-temperature lithium ion battery storage=(volume/lithium after high-temperature lithium ion battery storage Volume before ion battery high temperature storage) × 100%.
The data detected are as shown in table 1.
Table 1
Wherein, "/" represents and is not added with this material.
The performance test results analysis of lithium ion battery:
It can be seen that embodiment 1-6 is interpolation polyethylene in electrolyte from the contrast with comparative example 1-3 of embodiment 1-6 The lithium ion battery of ketopyrrolidine, compared with the lithium ion battery without the comparative example 1 of any additive, has preferable height Temperature cycle performance and high-temperature storage performance.
Comparative example 3 illustrates: when polyvinylpyrrolidone content in the electrolytic solution is more than 5%, its cycle performance occurs Deteriorating, it is blocked up that reason is probably the interfacial film that polyvinylpyrrolidone formed on both positive and negative polarity surface, have impact on lithium ion battery Cycle performance, but storage performance is improved the most further, this is because high-load polyvinylpyrrolidone coordination compound on the one hand can To form good interfacial film on both positive and negative polarity surface, reducing the reactivity of positive electrode surface, polyvinylpyrrolidone contains simultaneously There is substantial amounts of lewis base, the sour gas produced in storing process can be neutralized, such as PF5、HF、CO2Deng.Comparative example 2 illustrates: When polyvinylpyrrolidone weight/mass percentage composition < property when 0.1%, to lithium ion battery in the electrolyte of lithium ion battery The improvement of energy is inconspicuous.
As can be seen here, the lithium ion battery additive that the application provides can form good interface on both positive and negative polarity surface Film, reduces the reactivity of positive electrode surface, and suppression electrolyte is in the oxidation Decomposition of positive electrode surface；Utilize institute in this compound simultaneously The characteristic of the lewis base contained captures the acidic components and transition metal ions produced in the electrolytic solution, to improve battery at height High-temperature storage performance under voltage and cycle performance.
Embodiment 7～11
Preparing electrolyte and the lithium ion battery containing this electrolyte according to the method for embodiment 1, difference is: electrolyte In the structural formula of compound of additive and adding proportion as shown in table 2, the ratio of additive is with its containing in the electrolytic solution Amount calculates.
Table 2
Detecting according to the performance of the battery to preparing of the method in embodiment 1, detection obtains battery 7～11 Performance is similar to above example, repeats no more as space is limited.
Being above illustrating of presently preferred embodiments of the present invention, but the present invention is not limited to described embodiment, some becomes Shape or replacement compound are all contained in the application claim limited range.Additionally, it is specific to present invention uses some Term, but these terms are merely for convenience of description, and the present invention does not constitute any restriction.

Claims (10)

1. a lithium ion battery additive, it is characterised in that its at least one in compound shown in formula I:
Wherein, described R1、R2And R3It is each independently selected from hydrogen, substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C26Aryl, substituted or unsubstituted C5～C22Heterocyclic base, substituent group is halogen, n=90～3200；The most described R1、R2With R3For hydrogen or C1～C8Alkyl.
Additive the most according to claim 1, it is characterised in that the structural formula of described additive is as shown in Formula II:
3. a lithium ion battery, it contains positive plate, negative plate, isolating membrane and electrolyte, it is characterised in that described electrolysis Containing lithium salts, organic solvent and the additive described in claim 1 or 2 in liquid.
Lithium ion battery the most according to claim 3, it is characterised in that described additive and lithium salts be dissolved in respectively organic After solvent, it is implanted sequentially in lithium ion battery.
Lithium ion battery the most according to claim 4, it is characterised in that described organic solvent contains cyclic carbonate and chain Shape carbonic ester；Described cyclic carbonate is preferably selected from ethylene carbonate, Allyl carbonate, gamma-butyrolacton, sulfolane at least A kind of；Described linear carbonate is preferably selected from dimethyl carbonate, diethyl carbonate, dipropyl carbonate, Ethyl methyl carbonate, carbon In acid first propyl ester, ethyl propyl carbonic acid ester, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate At least one.
Lithium ion battery the most according to claim 4, it is characterised in that described lithium salts is selected from LiPF6、LiBF4、LiBOB、 LiDFOB、LiAsF6、LiClO4、LiFAP、LiCF3SO3、Li(FSO2)2N、Li(CF3SO2)2N、Li(C2F5SO2)2In N at least One, is more preferably selected from LiPF6、LiBF4、Li(FSO2)2At least one in N.
The preparation method of lithium ion battery the most according to claim 3, it is characterised in that include by described additive by with Under type adds:
Step one, described additive is dissolved in the first organic solvent obtains solution A, lithium salts is dissolved in the second organic solvent and obtains molten Liquid B；
Step 2, solution A is injected in lithium ion battery；And
Step 3, solution B is injected in lithium ion battery.
Method the most according to claim 7, it is characterised in that after step 2 terminates, stands 6～24h by lithium ion battery, Then step 3 is carried out；After preferred steps two terminates, lithium ion battery is stood at normal temperatures 6～24h, then at 50～70 DEG C Lower standing 6～24h, then carries out step 3.
Method the most according to claim 7, it is characterised in that described first organic solvent and the second organic solvent is identical or Difference is the most identical.
Method the most according to claim 7, it is characterised in that the content of described additive is the gross mass of solution A 0.1%～5%；Described lithium salts concentration in solution B is 1.5M～3M；
Preferably, described solution A is 0.5～2:1 with the mass ratio of solution B, more preferably 1:1.
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