CN109659598A - A kind of nickelic high capacity dynamic lithium battery - Google Patents

A kind of nickelic high capacity dynamic lithium battery Download PDF

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Publication number
CN109659598A
CN109659598A CN201811500518.6A CN201811500518A CN109659598A CN 109659598 A CN109659598 A CN 109659598A CN 201811500518 A CN201811500518 A CN 201811500518A CN 109659598 A CN109659598 A CN 109659598A
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CN
China
Prior art keywords
additive
high capacity
lithium battery
capacity dynamic
lithium
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Pending
Application number
CN201811500518.6A
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Chinese (zh)
Inventor
李菊香
郑春龙
钱国珠
刘涛
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JIANGSU TENPOWER LITHIUM CO Ltd
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JIANGSU TENPOWER LITHIUM CO Ltd
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Priority to CN201811500518.6A priority Critical patent/CN109659598A/en
Publication of CN109659598A publication Critical patent/CN109659598A/en
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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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—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
    • 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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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

Abstract

The invention discloses a kind of nickelic high capacity dynamic lithium batteries, including anode, cathode, diaphragm and electrolyte, positive electrode is selected from the rich nickel ternary material of lithium ion conductor coating modification, negative electrode material is selected from nitrating carbon coating silicon composite, the electrolyte includes lithium salts LiPF6, carbonate-based solvent and additive, the additive includes that SEI film for additive, overcharging additive, flame-retardant additive and high temperature performance improve additive, and the diaphragm is selected from ceramic coating modified diaphragm.Lithium battery prepared by the present invention has high security, long-life and rapid charging performance.

Description

A kind of nickelic high capacity dynamic lithium battery
Technical field
The present invention relates to a kind of nickelic high capacity dynamic lithium batteries, belong to EV technical field of lithium batteries.
Background technique
The raising of battery energy density depends on the exploitation of novel positive and negative electrode material.In lithium ion battery, positive electrode It occupys an important position, performance directly determines the performance indicator of final battery product.Cobalt acid lithium, LiMn2O4, ferric phosphate The materials such as lithium have been difficult to meet requirement of the next-generation new-energy automobile to lithium battery.Ternary material is especially with nickelic ternary material Positive electrode based on material is current and is researched and developed in 5 years from now on and the main trend of industrialization.High-capacity cathode material, it is special It is not silicon carbon material is most to have the high of industrialization at present to hold negative electrode material, home and abroad has begun batch and uses.This project The technology path that product adheres to high-nickel material and high capacity silicon carbon material is developed as battery gradually reaches high energy ratio, long continuation of the journey Battery performance, this is also the following inexorable trend for promoting energy.
Summary of the invention
The technical problem to be solved by the invention is to provide with high security, the long-life, rapid charging performance power lithium battery Pond.
In order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
A kind of nickelic high capacity dynamic lithium battery, including anode, cathode, diaphragm and electrolyte, positive electrode are selected from lithium The rich nickel ternary material of ion conductor coating modification, negative electrode material are selected from nitrating carbon coating silicon composite, the electrolyte packet Lithium salts LiPF6, carbonate-based solvent and additive are included, the additive includes SEI film for additive, overcharging additive, resistance Firing additive and high temperature performance improves additive, and the diaphragm is selected from ceramic coating modified diaphragm.
Rich nickel ternary material is Ni0.8Co0.1Mn0.1 in the rich nickel ternary material of the lithium ion conductor coating modification (OH)2；The chemical composition of lithium ion conductor is Li2MO3, and wherein M is one kind of Ti, Si or Zr；Li2MO3 accounts for anode after cladding The mass fraction of material is 1%~5%.
The nitrating carbon coating silicon composite includes mixing positioned at the silica-base material of composite inner and organic pyrolysis Nitrogen carbon coating layer, the presoma of the nitrating carbon coating layer are ionic liquid.
The SEI film for additive includes one in di-oxalate lithium borate, fluorinated ethylene carbonate or vinylene carbonate Kind is a variety of.
The weight percentage of the SEI film for additive in the electrolytic solution is 1%~5%.
The high-temperature behavior improves additive and is selected from difluorine oxalic acid boracic acid lithium.
The lithium salts electrolyte content is 0.5mol/L~2.0mol/L.
Advantageous effects of the invention:
Using nitrating carbon coating silicon composite as lithium ion battery negative material, which, which has, is preferably followed Ring stability and good large current density electrical characteristics；
What is used is used as positive electrode by Li2MO3 coating modification Ni0.8Co0.1Mn0.1 (OH) 2, can significantly improve High temperature circulation stability and high rate capability；
Electrolyte is main solvent by main salt, carbonic ester of LiPF6, improves positive electrode surface state, plays guarantor to active material Shield effect, selects SEI film for additive, improves the flexibility and adhesion strength that silicon-carbon cathode surface SEI is touched, especially fluoro carbon Vinyl acetate can be used for the cycle performance for improving battery；Addition overcharging additive and flame-retardant additive improve battery core safety Property, addition LIDOFB additive improves the high temperature performance of battery core；
Battery prepared by the present invention can achieve following technical indicator: high safety: monomer passes through GBT31485 safety requirements: Long-life: 25 DEG C of+0.5C/-1C@circulations 1500 times or more, capacity retention ratio 80%；High-energy-density: single battery energy density Reach 300Wh/Kg or more；Rapid charging performance: meet 30min charge volume 80%；Excellent cryogenic property :@- 20 DEG C of+0.5C/-1C 92% or more discharge capacitance；
Electrolyte system produced by the present invention has excellent compatibility to lithium ion battery positive and negative electrode material, is expected to It is applied in the extended-life lithium ion battery of high security.
Detailed description of the invention
Fig. 1 is embodiment capacity distribution map；
Fig. 2 is embodiment AC internal Resistance distribution map；
Fig. 3 is embodiment multiplying power temperature rise model figure (remarks: about 5-8 DEG C of 1C multiplying power temperature rise)；
Fig. 4 is the test of embodiment high temperature performance；
Fig. 5 is embodiment DC internal resistance distribution map；
Fig. 6 is embodiment cycle performance test result；
Fig. 7 is embodiment cycle performance test result.
Specific embodiment
The invention will be further described below in conjunction with the accompanying drawings.Following embodiment is only used for clearly illustrating the present invention Technical solution, and not intended to limit the protection scope of the present invention.
Electrolyte quota: the electrolysis that a certain amount of lithium hexafluoro phosphate makes it be formulated as 1mol/L is added into ethylene carbonate Then 2 weight %FEC, LIBOB, 3 weight % biphenyl, the 5 weight %TMP of electrolyte total weight, 5 weights are added in liquid thereto Amount %LIDOFB obtains required electrolyte after being uniformly mixed.
Anode preparation: by lithium ion conductor cladding Ni0.8Co0.1Mn0.1 (OH) 2 of 95 weight %, (preparation method has Body is shown in ZL201310322664.5) it is added as positive electrode active materials, the conductive agent of 2.5 weight % and 2.5 weight % binders Into n-methyl-2-pyrrolidone (NMP) solvent, to prepare cathode mix slurry.Thereafter, the anode sizing agent of formation is applied It is overlying on aluminium foil, and forms anode pole piece by rolling shearing after drying.
Cathode preparation: by the nitrating carbon coating silicon composite of 95 weight %, (preparation method is specifically shown in CN201510338749.1) binder as negative electrode active material, 2.5 weight % conductive agents and 2.5 weight % is added to In ionized water, to prepare negative electrode mix slurry.Thereafter, the negative electrode slurry of formation is coated on copper foil, and passes through drying After roll shearing and form cathode pole piece.
Diaphragm is ceramic coating modified diaphragm.
The following are EV lithium battery product main performance index is made using above-mentioned formula
(1) monomer capacity: 3.2Ah (0.2C)
(2) voltage range: 2.5-4.20V
(3) energy content of battery: >=250Wh/kg
(4) electric current:
◆ 3C (30s charging, 30s electric discharge)
◆ 30s pulse charging current (A) map is shown in Table 1
◆ 30s impulse discharge current (A) map is shown in Table 2
Table 1
Table 2
(5) pulse power
◆ 30s pulse charge power such as table 3
◆ 30s pulsed discharge power such as table 4
Table 3
Table 4
(6) cycle performance
◆ 25 DEG C of cycle life >=1000 time@, 100%DOD (+0.5C/-1C；2.75-4.2V)；
◆@- 10 DEG C of low-temperature circulating service life >=400 time, 100%DOD (+1C/-0.5C；2.75-4.2V)；
◆ big 25 DEG C of circulation service life >=600 time@, 100%DOD (+1C/-6A；3.0-4.2V).
(7) storge quality
◆ 100%SOC, 30 days, 25 DEG C, residual capacity >=90%；
◆ 100%SOC, 30 days, 40 DEG C, residual capacity >=88%；
◆ 100%SOC, is stored 300 days, internal resistance amplification < 50% by 60 DEG C.
(8) security performance
According to GBT31485 standard testing, reliability, durability and the safety of the actual use of our company product, in addition to needle thorn All by test, the requirement of Vehicular dynamic battery can satisfy, performance also reaches advanced international level)
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art For member, without departing from the technical principles of the invention, several improvement and deformations can also be made, these improvement and deformations Also it should be regarded as protection scope of the present invention.

Claims (7)

1. a kind of nickelic high capacity dynamic lithium battery, including anode, cathode, diaphragm and electrolyte, characterized in that positive electrode Rich nickel ternary material selected from lithium ion conductor coating modification, negative electrode material are selected from nitrating carbon coating silicon composite, the electricity Solving liquid includes lithium salts LiPF6, carbonate-based solvent and additive, and the additive includes SEI film for additive, overcharges addition Agent, flame-retardant additive and high temperature performance improve additive, and the diaphragm is selected from ceramic coating modified diaphragm.
2. a kind of nickelic high capacity dynamic lithium battery according to claim 1, characterized in that the lithium ion conductor cladding Rich nickel ternary material is Ni0.8Co0.1Mn0.1 (OH) 2 in modified rich nickel ternary material；The chemical composition of lithium ion conductor is Li2MO3, wherein M is one kind of Ti, Si or Zr；Li2MO3 account for cladding after positive electrode mass fraction be 1%~5%.
3. a kind of nickelic high capacity dynamic lithium battery according to claim 1, characterized in that the nitrating carbon coating silicon is multiple Condensation material includes the silica-base material and organic pyrolysis nitrating carbon coating layer positioned at composite inner, the nitrating carbon coating layer Presoma be ionic liquid.
4. a kind of nickelic high capacity dynamic lithium battery according to claim 1, characterized in that the SEI film for additive Including one of di-oxalate lithium borate, fluorinated ethylene carbonate or vinylene carbonate or a variety of.
5. a kind of nickelic high capacity dynamic lithium battery according to claim 1, characterized in that the SEI film for additive Weight percentage in the electrolytic solution is 1%~5%.
6. a kind of nickelic high capacity dynamic lithium battery according to claim 1, characterized in that the high-temperature behavior improvement adds Agent is added to be selected from difluorine oxalic acid boracic acid lithium.
7. a kind of nickelic high capacity dynamic lithium battery according to claim 1, characterized in that the lithium salts electrolyte content For 0.5mol/L~2.0mol/L.
CN201811500518.6A 2018-12-10 2018-12-10 A kind of nickelic high capacity dynamic lithium battery Pending CN109659598A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110534736A (en) * 2019-08-28 2019-12-03 电子科技大学 A kind of high potential lithium ion battery NCM tertiary cathode material and preparation method thereof
CN110931873A (en) * 2019-12-11 2020-03-27 中国科学院山西煤炭化学研究所 Lithium ion battery electrolyte suitable for high-nickel ternary/silicon-carbon system

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CN105859760A (en) * 2016-03-18 2016-08-17 汕头市金光高科有限公司 A synthetic method of electronic grade lithium difluoro(oxalato)borate
CN106252716A (en) * 2016-10-17 2016-12-21 东莞市凯欣电池材料有限公司 A kind of safe lithium ion power battery electrolyte and lithium-ion-power cell
CN107749464A (en) * 2016-11-02 2018-03-02 万向二三股份公司 A kind of energy density lithium ion power battery
CN108448083A (en) * 2018-03-09 2018-08-24 成都新柯力化工科技有限公司 A kind of lithium battery tertiary cathode material and preparation method of nucleocapsid

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Publication number Priority date Publication date Assignee Title
CN101771167A (en) * 2010-02-05 2010-07-07 九江天赐高新材料有限公司 High-capacity lithium-ion electrolyte, battery and preparation method of battery
CN102832389A (en) * 2012-09-25 2012-12-19 湖南长远锂科有限公司 High-nickel positive active material of surface-modified lithium ion battery and preparation method of positive active material
CN104347857A (en) * 2013-07-29 2015-02-11 华为技术有限公司 Lithium ion secondary cell cathode active material and preparation method thereof, lithium ion secondary cell cathode pole piece and lithium ion secondary cell
CN103618071A (en) * 2013-11-14 2014-03-05 中国科学院广州能源研究所 Carbon-silicon composite negative electrode material of lithium ion battery and preparation method thereof
CN105859760A (en) * 2016-03-18 2016-08-17 汕头市金光高科有限公司 A synthetic method of electronic grade lithium difluoro(oxalato)borate
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110534736A (en) * 2019-08-28 2019-12-03 电子科技大学 A kind of high potential lithium ion battery NCM tertiary cathode material and preparation method thereof
CN110931873A (en) * 2019-12-11 2020-03-27 中国科学院山西煤炭化学研究所 Lithium ion battery electrolyte suitable for high-nickel ternary/silicon-carbon system
CN110931873B (en) * 2019-12-11 2022-08-16 中国科学院山西煤炭化学研究所 Lithium ion battery electrolyte suitable for high-nickel ternary/silicon-carbon system

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Application publication date: 20190419