CN109428078A - Battery with a battery cell - Google Patents

Battery with a battery cell Download PDF

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Publication number
CN109428078A
CN109428078A CN201710744106.6A CN201710744106A CN109428078A CN 109428078 A CN109428078 A CN 109428078A CN 201710744106 A CN201710744106 A CN 201710744106A CN 109428078 A CN109428078 A CN 109428078A
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compound
battery
electrolyte
lithium
halogen
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CN201710744106.6A
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CN109428078B (en
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张翠平
韩昌隆
张明
张�浩
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Secondary Cells (AREA)

Abstract

The application relates to the field of energy storage materials, in particular to a battery. The battery comprises a positive pole piece, a negative pole piece, an isolating membrane and electrolyte, wherein the isolating membrane is arranged between the positive pole piece and the negative pole piece; the anode active material is a ternary anode material, and the additive comprises a cyclic phosphazene compound and fluorobisoxalato phosphate. The electrolyte in the battery can reduce the corrosion of HF to the positive interface and protect the positive interface; meanwhile, the increase of positive and negative interface impedance is inhibited, and the cycle storage life is prolonged, so that the high-voltage cycle performance and the high-temperature storage performance of the battery are improved.

Description

A kind of battery
Technical field
This application involves energy storage material fields, specifically, are related to a kind of battery.
Background technique
In the information age of rapid development, the demand to electronic products such as mobile phone, notebook, cameras increases year by year.Electricity Working power of the pond especially lithium ion secondary battery as electronic product has energy density height, memory-less effect, work electricity It presses the features such as high, is just gradually replacing traditional Ni-Cd, MH-Ni battery.
Tertiary cathode material has an advantages such as energy density is high, discharge voltage high and low temperature performance is good, but in the prevalence of with Lower two problems: first is that the cycle performance of battery is poor, it is not able to satisfy requirement of the people to long-life batteries, second is that battery is in height Flatulence has security risk, in addition capacity suppression ratio is very fast during high temperature storage than more serious during gentle storage.
Summary of the invention
To solve the above-mentioned problems, the applicant has carried out sharp study, as a result, it has been found that: when adding ring simultaneously in electrolyte Phosphazene compound and the double oxalic acid phosphate of fluoro, can be good at the high voltage cycle for improving the battery using tertiary cathode material Performance and high-temperature storage performance, to complete the application.
This application provides a kind of battery, including anode pole piece, cathode pole piece, it is placed in the anode pole piece and the cathode Isolation film and electrolyte between pole piece contain positive electrode active materials in the anode pole piece, and the electrolyte includes organic Solvent, electrolyte and additive；
The structural formula of the positive electrode active materials is LiaNixCoyMzO2, M is in Mn, Al, Zr, Ti, V, Mg, Fe, Mo, B At least one, 0.95≤a≤1.2, x > 0, y > 0, z > 0, and x+y+z=1；
The additive includes cyclic phosphazene compound and the double oxalic acid phosphate of fluoro；
The cyclic phosphazene compound is selected from least one of Formulas I compound represented；
Wherein, R11、R12、R13、R14、R15、R16It is each independently the C replaced selected from halogen, halogen1~C12Alkyl, halogen The C that element replaces1~C12Alkoxy；And R11、R13、R15In at least one be C1~C12Alkoxy.
The technical solution of the application at least has following beneficial effect:
The battery of the application uses ternary positive electrode active material, while by adding ring phosphonitrile chemical combination simultaneously in the electrolytic solution Object and the double oxalic acid phosphate of fluoro, reduce erosion of the HF to positive interface, protect positive interface；Positive and negative interface is inhibited simultaneously The increase of impedance is conducive to the improvement for recycling storage life, to improve the height of the battery using ternary positive electrode active material Voltage cycle performance and high-temperature storage performance.
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.
The embodiment of the present application provides a kind of battery, including anode pole piece, cathode pole piece, is placed in anode pole piece and cathode pole Isolation film and electrolyte between piece contain positive electrode active materials in anode pole piece, and electrolyte includes organic solvent, electrolyte And additive.The ingredient of the embodiment of the present application battery is illustrated one by one below.
[positive plate]
Contain positive electrode active materials in anode pole piece, the positive electrode active materials that the embodiment of the present application uses is tertiary cathode materials Material.Tertiary cathode material has the advantages such as energy density is high, discharge voltage high and low temperature performance is good, is suitable for power battery.Into one Step is optional, and the charge cutoff voltage of the embodiment of the present application battery is 4.2V~4.9V.
The structural formula of the embodiment of the present application tertiary cathode material is LiaNixCoyMzO2, M be selected from Mn, Al, Zr, Ti, V, Mg, At least one of Fe, Mo, B, 0.95≤a≤1.2, x > 0, y > 0, z > 0, and x+y+z=1；
Further alternative, the embodiment of the present application tertiary cathode material is selected from LiNi1/3Co1/3Mn1/3O2、 LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.5Co0.25Mn0.25O2In at least one Kind.
Positive plate further includes binder and conductive agent, will include the anode of positive electrode active materials, binder and conductive agent Slurry is coated on plus plate current-collecting body, obtains positive plate after anode sizing agent is dry.
[electrolyte]
In the electrolyte of the embodiment of the present application battery, additive includes cyclic phosphazene compound and the double oxalic acid phosphoric acid of fluoro Salt；Wherein, cyclic phosphazene compound is selected from least one of Formulas I compound represented；
Wherein, R11、R12、R13、R14、R15、R16It is each independently the C replaced selected from halogen, halogen1~C12Alkyl, halogen The C that element replaces1~C12Alkoxy；And R11、R13、R15In at least one be C1~C12Alkoxy.
During the quick charge of lithium ion battery, lithium ion is from just extremely fast deviating from, into electrolyte, pass through every Film carries out embedding lithium into cathode.In this case, lithium is high activity, therefore is easily reacted with cathode carbon, is generated Li2CO3, solid matters, these solid matters such as LiO, LiOH be covered on negative terminal surface, form a kind of " film ", i.e. solid electrolytic Matter interfacial film (Solid Electrolyte Interface, SEI film), excellent SEI film effectively can prevent solvent molecule from existing The lasting reduction reaction of electrode surface prevents solvation lithium ion to be embedded in graphite layers, to protect cathode.Therefore electrolyte Additive will facilitate to form a film in electrode surface.
With the use of high voltage and ternary positive electrode active material, it is necessary to improve electrolyte using suitable additive Dynamics and high temperature storage problem.In view of this, the embodiment of the present application in the electrolytic solution simultaneously added with cyclic phosphazene compound and The double oxalic acid phosphate of fluoro.Contain at least one alkoxy, alcoxyl in the cyclic phosphazene compound structure that the embodiment of the present application uses Base is electron donating group, can significantly increase the cloud density in ring phosphonitrile double bond, increase the nucleophilie nucleus ability of cyclic phosphazene compound, Electrophilic addition reaction occurs for the HF and N=P double bond for being more advantageous to electrolyte side reaction generation, and then removes HF, to reduce HF Erosion to positive interface, indirect protection anode interface.
The increase of DCR in circulation storing process mostlys come from electrolyte at positive and negative anodes interface and side reaction occurs, generates By-product deposition in electrode surface, the impedance of by-product is generally all bigger, therefore the total DCR for showing battery becomes larger, It can participate in forming a film at positive and negative anodes interface containing the double oxalic acid phosphate of fluoro simultaneously in the electrolyte of the embodiment of the present application, and at Film is more stable, it is sufficient to inhibit the decomposition of electrolyte in following cycle storing process, therefore inhibit DCR in circulation storing process Increase, improve the dynamic performance of system.
To sum up, cyclic phosphazene compound and the double oxalic acid phosphate of fluoro are used in combination, and reduce erosion of the HF to positive interface, protect Positive interface is protected, so that storage performance of the battery of tertiary cathode material under high voltage condition can be improved；It inhibits simultaneously The increase of positive and negative interface impedance, to be more advantageous to the improvement of circulation storage life.
It is further alternative, in Formulas I, R11、R12、R13、R14、R15、R16It is each independently and replaces selected from halogen, halogen C1~C6The C that alkyl, halogen replace1~C6Alkoxy；And R11、R13、R15In at least one be C1~C6Alkoxy.
It is further alternative, in Formulas I, R11、R12、R13、R14、R15、R16It is each independently and replaces selected from halogen, halogen C1~C3The C that alkyl, halogen replace1~C3Alkoxy；And R11、R13、R15In at least one be C1~C6Alkoxy.
In Formulas I compound represented, the alkyl or alkoxy that halogen replaces include that part replaces, i.e. alkyl or alkoxy On hydrogen moiety be optionally substituted by halogen；The alkyl or alkoxy that halogen replaces also include whole substitutions, i.e. alkyl or alkoxy On hydrogen atom be all optionally substituted by halogen；
Halogen can be selected from fluorine, chlorine, bromine, and preferably fluorine.
Further alternative, cyclic phosphazene compound is selected from least one of compound shown in following structural formula, and unlimited In this:
Further alternative, the double oxalic acid phosphate of fluoro are selected from least one of Formula II compound represented；
Wherein, R21、R22It is each independently the C replaced selected from halogen, halogen1~C12The C that alkyl, halogen replace1~C12 Alkoxy；
A+Indicate lithium ion, sodium ion or potassium ion, preferably lithium ion.
It is further alternative, R21、R22It is each independently the C replaced selected from halogen, halogen1~C6Alkyl, halogen replace C1~C6Alkoxy.
Further alternative, the double oxalic acid phosphate of fluoro are selected from least one of compound shown in following structural formula；
(the double oxalic acid lithium phosphates of bis trifluoromethyl, compound B-11)；
(the double oxalic acid lithium phosphates of double difluoromethyls, compound B2)；
(the double oxalic acid lithium phosphates of difluoro, compound B3)；
(the double oxalic acid lithium phosphates of double pentafluoroethyl groups, compound B4).
Further alternative, mass percentage of the cyclic phosphazene compound in the electrolyte is 0.001%~3%. If cyclic phosphazene compound content is too low, it is difficult to inhibit hydrogen fluoride, it is unobvious to the improvement of electrolyte, if ring phosphonitrile Compound is excessively high, can deteriorate the cycle performance of battery.
The upper limit of the mass percentage range of the embodiment of the present application cyclic phosphazene compound in the electrolytic solution optionally from 3%, 2.5%, 2%, 1.8%, 1.6%, 1.5%, 1.3%, 1.2%, 1%, 0.8%, 0.6%, lower limit optionally from 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.3%, 0.5%.It is further preferred that cyclic phosphazene compound is in the electrolytic solution Percentage composition be 0.1%~2%.
It is further alternative, double mass percentages of the oxalic acid phosphate in the electrolyte of fluoro are 0.001%~ 3%.If the double oxalic acid phosphate contents of fluoro are too low, unobvious to the improvement of anode, if the double oxalic acid phosphoric acid of fluoro Salt is excessively high, and the performance of battery is not promoted linearly.
The upper limit of the mass percentage range of the double oxalic acid phosphate of the embodiment of the present application fluoro in the electrolytic solution is optionally certainly 3%, 2.5%, 2%, 1.8%, 1.6%, 1.5%, 1.3%, 1.2%, 1%, 0.8%, 0.6%, lower limit is optionally certainly 0.001%, 0.005%, 0.01%, 0.05%, 0.1%, 0.3%, 0.5%.It is further preferred that the double oxalic acid phosphoric acid of fluoro The percentage composition of salt in the electrolytic solution is 0.1%~2%.
In the electrolyte of the embodiment of the present application, electrolyte is not selected from the double oxalic acid phosphate of fluoro.
When battery is lithium ion battery, electrolyte is selected from lithium hexafluoro phosphate, bis- (trifluoromethyl) sulfimide lithiums, tetrafluoro At least one of lithium borate, trifluoromethyl sulfonic acid lithium, hexafluoroarsenate lithium, di-oxalate lithium borate, lithium perchlorate, more preferably six Lithium fluophosphate.
In the electrolyte of the embodiment of the present application, other additives can also be contained, including but not limited to:
1, dinitrile compound: it is selected from least one of compound as shown in formula III -1；
Wherein, R31Selected from substituted or unsubstituted C1~C12Alkylidene；Substituent group is selected from halogen, C1~C3Alkyl, C2~C4 Alkenyl.
Specifically, dinitrile compound can be selected from least one of glutaronitrile, adiponitrile, however it is not limited to this.
Dinitrile compound is due to that can stablize cathode material by complexing with negatively charged cyano (CN-) Metal ion, inhibit the dissolution of metal ion, so as to improve the electrical property of battery.
2, containing the cyclic carbonate compound of unsaturated bond: being selected from least one of compound as shown in formula III -2；
R32The C replaced selected from alkenyl1~C6Alkylidene, substituted or unsubstituted C2~C6Alkenylene.
Cyclic carbonate compound containing unsaturated bond is selected from least one of following compound, and concrete structure formula is such as Under:
It is poly- that in anode reduction reaction generation can occur for the double bond that the cyclic carbonate compound containing unsaturated bond contains Closing object protective film is the generation for participating in SEI film.
3, cyclic sulfates compound: being selected from least one of compound as shown in formula III -3,
R33Selected from substituted or unsubstituted C1~C6Alkylidene, substituted or unsubstituted C2~C6Alkenylene, substituent group are selected from Halogen, C1~C3Alkyl, C2~C4Alkenyl.
Cyclic sulfates compound is selected from sulfuric acid vinyl ester (referred to as DTD), sulfuric acid acrylic ester (referred to as TMS), 4- first At least one of base ethyl sulfate (referred to as PLS), concrete structure formula is as follows；
Cyclic sulfates compound is preferable positive and negative anodes interface film for additive, can reduce into membrane impedance.
4, sultone compounds: it is selected from least one of compound as shown in formula III -4；
Wherein, R34Selected from substituted or unsubstituted C1~C6Alkylidene, substituted or unsubstituted C2~C6Alkenylene replaces Base is selected from halogen, C1~C3Alkyl, C2~C4Alkenyl.
Specifically, sultone compounds are selected from 1,3- propane sultone (referred to as PS), 1,3- propene sultone At least one of (referred to as PES), concrete structure formula is as follows；
Sultone compounds may participate in positive and negative anodes film forming, so that significantly inhibiting high temperature storage produces gas.
5, difluorophosphate:
Difluorophosphate participates in positive interface film forming, and it is more stable to form a film, so as to improve the high temperature storage of battery Energy.
The dosage of above-mentioned additive is can be between 0.01%~3%.
In the electrolyte of the embodiment of the present application, organic solvent is non-aqueous organic solvent, and organic solvent is chosen as carbon atom Number is 1~8 and the compound containing at least one ester group, is further selected from ether compound.
Specific optional, organic solvent is selected from C1~C8Linear carbonate, C1~C8Cyclic carbonate, C1~C8Chain carboxylic Acid esters, ring C1~C8Cyclic carboxylic esters, C2~C8At least one of ether.
As C1~C8The example of linear carbonate can be enumerated: methyl ethyl carbonate, dimethyl carbonate, diethyl carbonate, carbon At least one of sour dipropyl, methyl propyl carbonate and ethyl propyl carbonic acid ester；
As C1~C8The example of cyclic carbonate can be enumerated: ethylene carbonate, propene carbonate, butylene and fluorine For at least one of ethylene carbonate；
As C1~C8The example of chain carboxylate can be enumerated: methyl propionate, methyl butyrate, ethyl acetate, ethyl propionate At least one of with ethyl butyrate；
As C1~C8The example of cyclic carboxylic esters can be enumerated: 1,4-butyrolactone.
As C2~C8The example of ether can enumerate tetrahydrofuran.
In the embodiment of the present application, C can be used in organic solvent1~C8Linear carbonate and C1~C8Cyclic carbonate shares Organic solvent.
The organic solvent that further optional ethylene carbonate (EC) and diethyl carbonate (DEC) share.
In the embodiment of the present application, the preparation method of electrolyte selects conventional method, such as can be by organic solvent, lithium Salt and additive are uniformly mixed.
[negative electrode tab]
Contain negative electrode active material, binder and conductive agent in negative electrode tab, wherein negative electrode active material can be selected from hard The carbon materials such as carbon, natural graphite, artificial graphite, soft carbon, carbon black, acetylene black, carbon nanotube, graphene, carbon nano-fiber.This Outside, it as other negative electrode active materials, can also enumerate such as Si, Ge, Pb, In, Zn, H, Ca, Sr, Ba, Ru, Rh and sodium Simple substance, the oxide containing these elements and the carbide of element etc. of alloying occurs.But these materials are not limited to, it can To use the conventional known material for being used as sodium ion battery negative.These negative electrode active materials can be only single Solely using one kind, can also be used in combination of two or more.
It will include that the negative electrode slurry of negative electrode active material, binder and conductive agent is coated on negative current collector, to negative Negative electrode tab is obtained after pole slurry is dry.
[diaphragm]
In above-mentioned battery, the specific type of diaphragm is not exposed to specific limitation, can be used in existing battery Any diaphragm material, such as polyethylene, polypropylene, Kynoar and their multilayer complex films, but it is not limited only to these.
Below with reference to embodiment, further description of the technical solution of the present invention, and however, it is not limited to this, all right Technical solution of the present invention is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be contained Lid is within the protection scope of the present invention.
In following embodiments, comparative example, reagent, material and the instrument used such as not special explanation, Commercially available or synthesis obtains.Specific used reagent is as follows:
Additive:
Cyclic phosphazene compound: the compound A1~A4 being previously mentioned；The double oxalic acid phosphate of fluoro: the compound being previously mentioned B1~B4；Other additives: glutaronitrile, ethyl sulfate (DTD), vinylene carbonate (VC), 1,3- propane sultone (PS), difluorophosphate；
Lithium salts: lithium hexafluoro phosphate (LiPF6)。
Organic solvent: ethylene carbonate (EC), diethyl carbonate (DEC).
Positive electrode active materials: cobalt nickel lithium manganate ternary material.
Isolation film: using 16 μm of polyethylene porous thin polymer film (PE) as isolation film.
(1) preparation of electrolyte
In the glove box full of argon gas (water content < 10ppm, oxygen content < 1ppm), by additive according to certain Mass ratio is added in non-aqueous organic solvent, and other appropriate additives are added, after mixing, to non-aqueous organic solvent (EC: DEC=3:7 suitable lithium salts (LiPF is slowly added in)6), after lithium salts is completely dissolved, obtaining lithium salt is 1mol/L's Electrolyte, the as described electrolyte.
(2) preparation of positive plate:
By positive electrode active materials, conductive agent Super P, binder polyvinylidene fluoride (PVDF) in N-Methyl pyrrolidone (NMP) anode sizing agent is made in.Solid content is 50wt%, positive electrode active materials, Super in solid component in anode sizing agent P, the mass ratio of PVDF is 6:2:2:2.Anode sizing agent is coated in current collector aluminum foil and is cold-pressed after being dried at 85 DEG C, Then after carrying out trimming, cut-parts, slitting, 4h is dried under 85 DEG C of vacuum condition, positive plate is made.
(3) preparation of negative electrode tab:
It will be as the graphite of negative electrode active material and conductive agent Super P, thickener CMC, bonding agent butadiene-styrene rubber (SBR) It is uniformly mixed in deionized water, negative electrode slurry is made.Solid content is 53wt% in negative electrode slurry, graphite in solid component, The mass ratio of Super P, CMC and bonding agent butadiene-styrene rubber (SBR) is 6:2:2:2.Negative electrode slurry is coated on copper foil of affluxion body It above and at 85 DEG C dries, is then cold-pressed, after trimming, cut-parts, slitting, dries 12h under 120 DEG C of vacuum conditions, be made Negative electrode tab.
(4) preparation of lithium ion battery:
Positive plate obtained, isolation film, negative electrode tab are folded in order, make isolation film be among positive/negative plate play every Effect from positive and negative anodes, winding obtain naked battery core, and naked battery core is placed in outer packing by soldering polar ear, by the electrolysis of above-mentioned preparation Liquid is injected into the battery core after drying, and encapsulation, standing, chemical conversion, shaping, volume test etc., the preparation for completing lithium ion battery is (soft Thickness 4.0mm, the width 60mm, length 140mm of packet lithium ion battery).
In embodiment 1-20 and comparative example 1-5, used solvent and additives ratio are as shown in table 1, wherein in table Additives ratio is that the gross mass based on electrolyte calculates obtained mass percent in 1；Positive electrode active materials in positive plate As shown in table 1.
Table 1
Note: any substance is not added in "/" expression.
The test process of lithium ion battery will be illustrated next.
(1) the cycle performance test of lithium ion battery
Under room temperature, by lithium ion battery with 4C constant-current charge to 4.2V, then it is with 4.2V constant-voltage charge to electric current 0.05C, then with 1C constant-current discharge to 2.8V, this is a charge and discharge cycles.Capacity to discharge for the first time calculates for 100% Capacity retention ratio after lithium ion battery circulation 300 times.Capacity retention ratio (%)=the after lithium ion battery circulation 300 times The discharge capacity of 300 circulations/capacity × 100% that discharges for the first time.
(2) high-temperature lithium ion battery gas generation property is tested
Under room temperature, by lithium ion battery with 1C constant-current charge to 4.2V, then extremely with the voltage constant-voltage charge of 4.2V Electric current is 0.05C, after battery completely fills, tests battery volume using drainage, and record, battery is placed at 80 DEG C and is stored, 24 After hour, battery is taken out, at room temperature, 60min is stood, uses drainage test volume in 1 hour after being cooled to room temperature, And record, later by above-mentioned steps storage test, until storage 30 days.Battery volume to test before storing is counted as benchmark Calculate the cubical expansivity that battery changes with storage time.
Lithium ion battery is at 80 DEG C, cubical expansivity (%) after storing different number of days=(measure after storing for the N days The battery volume measured before battery volume/storage) -1.
(3) 60 DEG C of storage life tests of lithium ion battery
Under the conditions of 60 DEG C, lithium ion battery is charged to 4.2V with 1C, is then to electric current with 4.2V constant-voltage charge 0.05C surveys the capacity of battery later every 30 days, on the basis of the capacity measured for the first time, capacity holding (%)=the Capacity × 100% for the capacity that n times are tested/measure for the first time.
The storage of 2 high-temperature lithium ion battery of table produces gas and capacity retention ratio
By the test result of table 1 it is known that the capacity after producing gas, circulation with the storage that comparative example 1-5 is tested is protected Capacity retention ratio after holdup, storage is compared, and the properties of embodiment 1-20 are significantly improved, and is illustrated with alcoxyl The double oxalic acid lithium phosphates of the cyclic phosphazene compound and fluoro of base are used in combination, and can form metastable interface at positive and negative anodes interface Film can effectively improve the dynamic performance of battery in turn.
According to embodiment 1-6 it is found that when the double oxalic acid phosphate contents of fluoro are gradually increased, properties specifically have by Gradually improve.The double oxalic acid phosphoric acid lithium contents of fluoro are more in comparative example 4, and oxidizable generation side reaction under high temperature deteriorates high temperature storage Performance.Simultaneously because the double oxalic acid phosphoric acid lithium contents of fluoro are very little in embodiment 1, complete interfacial film can not be formed in positive and negative anodes, It is limited to the improvement result of battery performance.
According to embodiment 7-12 it is found that when the cyclic phosphazene compound content with alkoxy is gradually increased, items It can be gradually increased.Cyclic phosphazene compound content is more in comparative example 5, causes electrolyte viscosity bigger, deteriorates electrolyte Dynamic performance.Five fluorine ring phosphonitrile content of alkoxy is less in embodiment 7, is not enough to remove the hydrofluoric acid generated in electrolyte, It is limited to the improvement result of battery performance.
Comparative example 2 is individually added into the double oxalic acid lithium phosphates of fluoro can not inhibit although it can form a film at positive interface The hydrogen fluoride of generation in electrolyte is unable to hydrogen fluoride and inhibits to destroy electrode interface and deteriorate battery performance.
Comparative example 3 is individually added into the cyclic phosphazene compound with alkoxy, although HF can be captured, inhibits electrolyte to electricity The erosion at pole interface, but due to anode do not form good interfacial film, can not effectively inhibit the generation of side reaction, because This room temperature cycles performance is poor.
It is not for limiting claim, any this field skill although the application is disclosed as above with preferred embodiment 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 the claim of this application is defined.

Claims (10)

1. a kind of battery, including anode pole piece, cathode pole piece, the isolation being placed between the anode pole piece and the cathode pole piece Film and electrolyte contain positive electrode active materials in the anode pole piece, and the electrolyte includes organic solvent, electrolyte and adds Add agent；
It is characterized in that,
The structural formula of the positive electrode active materials is LiaNixCoyMzO2, M in Mn, Al, Zr, Ti, V, Mg, Fe, Mo, B extremely Few one kind, 0.95≤a≤1.2, x > 0, y > 0, z > 0, and x+y+z=1；
The additive includes cyclic phosphazene compound and the double oxalic acid phosphate of fluoro；
The cyclic phosphazene compound is selected from least one of Formulas I compound represented；
Wherein, R11、R12、R13、R14、R15、R16It is each independently the C replaced selected from halogen, halogen1~C12Alkyl, halogen take The C in generation1~C12Alkoxy；And R11、R13、R15In at least one be C1~C12Alkoxy.
2. battery according to claim 1, which is characterized in that the double oxalic acid phosphate of the fluoro are shown in the Formula II At least one of compound；
Wherein, R21、R22It is each independently the C replaced selected from halogen, halogen1~C12The C that alkyl, halogen replace1~C12Alcoxyl Base；
A+Indicate lithium ion, sodium ion or potassium ion, preferably lithium ion.
3. battery according to claim 1, which is characterized in that the cyclic phosphazene compound is selected from following structural formula shownization Close at least one of object；
4. battery according to claim 1, which is characterized in that the double oxalic acid phosphate of the fluoro are selected from following structural formula institute Show at least one of compound；
5. battery according to claim 1, which is characterized in that quality of the cyclic phosphazene compound in the electrolyte Percentage composition is 0.001%~3%, preferably 0.1%~2%.
6. battery according to claim 1, which is characterized in that the double oxalic acid phosphate of the fluoro are in the electrolyte Mass percentage is 0.01%~3%, preferably 0.1%~2%.
7. battery according to claim 1, which is characterized in that the electrolyte is selected from lithium hexafluoro phosphate, bis- (fluoroforms Base) sulfimide lithium, LiBF4, trifluoromethyl sulfonic acid lithium, hexafluoroarsenate lithium, di-oxalate lithium borate, in lithium perchlorate At least one, preferably lithium hexafluoro phosphate.
8. battery according to claim 1, which is characterized in that further include dinitrile compound in the additive, containing not The cyclic carbonate compound of saturated bond, cyclic sulfates compound, sultone compounds, at least one in difluorophosphate Kind；
Preferably, the dinitrile compound is selected from least one of such as -1 compound represented of formula III, described to contain unsaturation The cyclic carbonate compound of key is selected from least one of compound as shown in formula III -2, the cyclic sulfates compound Selected from least one of compound as shown in formula III -3, the sultone compounds are selected from the compound as shown in formula III -4 At least one of；
Wherein, R31Selected from substituted or unsubstituted C1~C12Alkylidene,
R32The C replaced selected from alkenyl1~C6Alkylidene, substituted or unsubstituted C2~C6Alkenylene,
R33、R34It is independently selected from substituted or unsubstituted C1~C6Alkylidene, substituted or unsubstituted C2~C6Alkenylene,
Substituent group is selected from halogen, C1~C3Alkyl, C2~C4Alkenyl.
9. battery according to claim 8, which is characterized in that the dinitrile compound is in glutaronitrile, adiponitrile At least one, the cyclic carbonate compound containing unsaturated bond are selected from vinylethylene carbonate, the cyclic sulfates Compound is selected from sulfuric acid vinyl ester, and the sultone compounds are selected from 1,3- propene sultone.
10. battery according to claim 1, which is characterized in that the charge cutoff voltage of the battery is not less than 4.2V.
CN201710744106.6A 2017-08-25 2017-08-25 Battery with a battery cell Active CN109428078B (en)

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WO2021023131A1 (en) * 2019-08-08 2021-02-11 宁德时代新能源科技股份有限公司 Electrolyte, lithium ion battery and device
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