CN106099192A - Utilize the electrolyte preventing box hat from corroding prepared by sulfenyl tetrazole compound - Google Patents
Utilize the electrolyte preventing box hat from corroding prepared by sulfenyl tetrazole compound Download PDFInfo
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- CN106099192A CN106099192A CN201610694319.8A CN201610694319A CN106099192A CN 106099192 A CN106099192 A CN 106099192A CN 201610694319 A CN201610694319 A CN 201610694319A CN 106099192 A CN106099192 A CN 106099192A
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- sulfenyl
- box hat
- electrolyte
- tetrazole compound
- corroding
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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
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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
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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
- H01M10/0569—Liquid materials characterised by the solvents
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
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- 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)
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- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
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- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of electrolyte preventing box hat from corroding utilizing sulfenyl tetrazole compound to prepare, according to mass percent, be made up of organic solvent 86 90%, lithium hexafluoro phosphate 7 9% and sulfenyl tetrazole compound 3 5%；Organic solvent, according to mass percent, is made up of wire carboxylate solvent 25 40% and aromatic hydrocarbon solvent 60 75%；The structural formula of sulfenyl tetrazole compound is as follows:Wherein, R1‑R2Any one in hydrogen, halogen, the alkyl of C1 C6 and haloalkyl thereof, the itrile group of C1 C4, the thiazolinyl of C2 C6, alkoxyl, carboxyl, phenyl ring, halogeno-benzene, R1‑R2At least one is C1 C4 itrile group or carboxyl.The present invention has the anticorrosion ability of excellence by the electrolyte that sulfenyl tetrazole compound and organic solvent, lithium hexafluoro phosphate are configured to, and the lithium ion battery applying this electrolyte to make has preferable market prospect.
Description
Technical field
The present invention relates to cell art, a kind of utilize prepared by sulfenyl tetrazole compound to prevent box hat
The electrolyte of corrosion.
Background technology
In the production process of lithium ion battery, to battery inject this operation of electrolyte inevitable that residual
Electrolyte is present in battery surface, if erasing these electrolyte remained clean can not be wiped in time or fail, treats battery
Produce glove box and be positioned under open environment, the electrolyte of residual will rapidly and air reaction generate deep-etching material, this
The appearance of box hat battery will be caused corrosion by the existence of a little strong corrosive materials, thus causes battery bad order, serious
Even scrap.
For the above-mentioned box hat etching problem brought due to fluid injection, it is presently mainly the electricity by wiping box hat remained on surface
Solution liquid and the method cleaned by abluent reach to prevent the purpose of electrolytic corrosion box hat.If but erasing not in time or
Fluid injection is long to the time interval cleaned, and corrosion is still inevitably generated, and so certainly will will waste substantial amounts of manpower and materials.
In recent years, flourish, to lithium ion battery along with the continuous renewal of digital product and electric vehicle
The performance such as service life, high temperature performance, safety, multiplying power proposes the highest requirement, a lot of people for this to lithium
Ion battery material carries out substantial amounts of R&D work, has made brilliant achievements.Existing lithium-ion battery electrolytes has raising lithium ion
The purposes such as the cycle life of battery and high temperature performance, but do not find that it possesses the purposes preventing box hat from corroding.
Therefore, need badly work out a kind of be prevented from box hat corrosion lithium-ion battery electrolytes.
Summary of the invention
It is an object of the invention to provide a kind of electricity preventing box hat from corroding utilizing sulfenyl tetrazole compound to prepare
Solve liquid, worked in coordination with by the sulfenyl tetrazole compound of certain proportioning and organic solvent, lithium hexafluoro phosphate and given play to the anti-of excellence
Corrosive effect.
For achieving the above object, the present invention provides following technical scheme:
Utilize the electrolyte preventing box hat from corroding prepared by sulfenyl tetrazole compound, according to mass percent, by
Organic solvent 86-90%, lithium hexafluoro phosphate 7-9% and sulfenyl tetrazole compound 3-5% composition；Described organic solvent is pressed
According to mass percent, it is made up of wire carboxylate solvent 25-40% and aromatic hydrocarbon solvent 60-75%；Described sulfenyl four nitrogen
The structural formula of azole compounds is as follows:
Wherein, R1-R2Selected from hydrogen, halogen, the alkyl of C1-C6 and haloalkyl thereof, the itrile group of C1-C4, the thiazolinyl of C2-C6,
Any one in alkoxyl, carboxyl, phenyl ring, halogeno-benzene, R1-R2At least one is C1-C4 itrile group or carboxyl.
As the further scheme of the present invention: according to mass percent, by organic solvent 88-90%, lithium hexafluoro phosphate
7-8% and sulfenyl tetrazole compound 3-4% composition；Described organic solvent is according to mass percent, by wire carboxylic acid
Ester solvent 32-35% and aromatic hydrocarbon solvent 65-68% composition.
As the further scheme of the present invention: according to mass percent, by organic solvent 88%, lithium hexafluoro phosphate 8%
Form with sulfenyl tetrazole compound 4%；Described organic solvent is according to mass percent, by wire carboxylate solvent
32% and aromatic hydrocarbon solvent 68% form.
As the further scheme of the present invention: described wire carboxylate solvent is ethyl propionate, n propyl propionate, acetic acid
Any one or two or more mixture in n-propyl, n-butyl acetate and isobutyl acetate.
As the further scheme of the present invention: described aromatic hydrocarbon solvent is benzene, fluorobenzene, difluoro-benzene, toluene, three fluoro
Any one or two or more mixture in benzene and dimethylbenzene.
The preparation method of the described electrolyte preventing box hat from corroding utilizing sulfenyl tetrazole compound to prepare, specifically
Step is as follows:
(1) in proportion wire carboxylate solvent and aromatic hydrocarbon solvent are mixed, use 5AoMolecular sieve, calcium hydride, lithium hydride are pure
Eliminate miscellaneous, except water, obtain organic solvent；
(2) at ambient temperature, in proportion lithium hexafluoro phosphate is dissolved in the organic solvent of step (1), stirs；
(3) it is proportionally added into sulfenyl tetrazole compound, prepares the required sulfenyl tetrazole compound that utilizes and prepare
Prevent the electrolyte that box hat corrodes.
The application in terms of making the lithium ion battery preventing box hat from corroding of the described electrolyte, this prevents box hat from corroding
Lithium ion battery is by positive electrode active materials, negative active core-shell material, barrier film and described utilizes sulfenyl tetrazole compound system
The standby electrolyte preventing box hat from corroding composition.
As the further scheme of the present invention: described positive electrode active materials includes metal composite oxide and the formula of lithium
For LiMx(PO4)yCompound；The metal composite oxide of described lithium includes nickel, cobalt, manganese element and the combination of any ratio thereof
Oxide；Described formula is LiMx(PO4)yCompound, M is the one in Ni, Co, Mn, Fe, Ti, V；0≤x≤5,0
≤y≤5。
As the further scheme of the present invention: described negative active core-shell material is lithium metal, the oxide of silicon, the oxidation of stannum
Any one or two or more mixture in thing, crystalline carbon or agraphitic carbon；Described crystalline carbon is native graphite, graphite
Change in coke, graphitized intermediate-phase carbosphere graphite, graphitized intermediate-phase asphalt-based carbon fiber any one or two or more
Mixture；Described barrier film is polyolefin porous membrane.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention is organic molten with the mixture that wire carboxylate solvent and aromatic hydrocarbon solvent are configured to according to a certain ratio
Agent, with lithium hexafluoro phosphate as lithium salts, with sulfenyl tetrazole compound as additive, prepares and a kind of is possible to prevent box hat to corrode
Electrolyte.On the one hand, this additive can constantly react with the strong corrosive material in electrolyte, makes box hat deposit at electrolyte
Remain to keep the state of light time long-time.On the other hand, this additive can also have precedence over electrolysis at the electrode surface of battery
Liquid reacts formation interfacial film, improves electrode/electrolyte interfacial property, suppression electrolyte electrode material surface oxidation or
Person's reduction decomposition, improves the compatibility of electrolyte and electrode, and can reduce the metal composite oxide of lithium and formula is
LiMx(PO4)yCompound dissolution from positive pole, metal composite oxide and the formula of suppression lithium are LiMx(PO4)yChemical combination
Thing deposition on negative pole and reduction, shield electrode material.
The present invention is directed to the respective materialization feature of organic solvent, lithium hexafluoro phosphate and sulfenyl tetrazole compound, make sulfur
Base tetrazole compound and organic solvent, lithium hexafluoro phosphate are after suitable proportioning, and can play respective advantage again can phase
Suppress mutually respective shortcoming, given play to the anticorrosion ability of excellence by the synergism between three, and the preparation of the present invention
Technique is the most easy to implement, has preferable market prospect.
Detailed description of the invention
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, all
Belong to the scope of protection of the invention.
Embodiment 1
In the embodiment of the present invention, utilize the electrolyte preventing box hat from corroding prepared by sulfenyl tetrazole compound, according to
Mass percent, is made up of organic solvent 86%, lithium hexafluoro phosphate 9% and sulfenyl tetrazole compound 5%；Organic solvent
According to mass percent, it is made up of wire carboxylate solvent 25% and aromatic hydrocarbon solvent 75%；Specifically, sulfenyl tetrazole
Compound is 5-methyl mercapto tetrazole, and structural formula is as follows:Wire carboxylate solvent is n-propyl acetate；Virtue
Fragrant hydrocarbon solvent is toluene.
Embodiment 2
In the embodiment of the present invention, utilize the electrolyte preventing box hat from corroding prepared by sulfenyl tetrazole compound, according to
Mass percent, is made up of organic solvent 90%, lithium hexafluoro phosphate 7% and sulfenyl tetrazole compound 3%；Organic solvent
According to mass percent, it is made up of wire carboxylate solvent 40% and aromatic hydrocarbon solvent 60%；Specifically, sulfenyl tetrazole
Compound is 5-ethylmercapto group tetrazole, and structural formula is as follows:Wire carboxylate solvent is ethyl propionate；Aromatic hydrocarbon
Solvent is dimethylbenzene.
Embodiment 3
In the embodiment of the present invention, utilize the electrolyte preventing box hat from corroding prepared by sulfenyl tetrazole compound, according to
Mass percent, is made up of organic solvent 88%, lithium hexafluoro phosphate 8% and sulfenyl tetrazole compound 4%；Organic solvent
According to mass percent, it is made up of wire carboxylate solvent 35% and aromatic hydrocarbon solvent 65%；Specifically, sulfenyl tetrazole
Compound is 5-benzylthio tetrazole, and structural formula is as follows:Wire carboxylate solvent is propanoic acid positive third
Ester；Aromatic hydrocarbon solvent is trifluoro-benzene.
Embodiment 4
In the embodiment of the present invention, utilize the electrolyte preventing box hat from corroding prepared by sulfenyl tetrazole compound, according to
Mass percent, is made up of organic solvent 90%, lithium hexafluoro phosphate 7% and sulfenyl tetrazole compound 3%；Organic solvent
According to mass percent, it is made up of wire carboxylate solvent 32% and aromatic hydrocarbon solvent 68%；Specifically, sulfenyl tetrazole
Compound is 5-sulfydryl-1-phenyl tetrazole, and structural formula is as follows:Wire carboxylate solvent is the positive fourth of acetic acid
Ester；Aromatic hydrocarbon solvent is difluoro-benzene.
Embodiment 5
In the embodiment of the present invention, utilize the electrolyte preventing box hat from corroding prepared by sulfenyl tetrazole compound, according to
Mass percent, is made up of organic solvent 88%, lithium hexafluoro phosphate 8% and sulfenyl tetrazole compound 4%；Organic solvent
According to mass percent, it is made up of wire carboxylate solvent 32% and aromatic hydrocarbon solvent 68%；Specifically, sulfenyl tetrazole
Compound is 5-sulfydryl-1-phenyl tetrazole, and structural formula is as follows:Wire carboxylate solvent is Sucrose Acetate
Ester；Aromatic hydrocarbon solvent is benzene.
In above-described embodiment, the described electrolyte preventing box hat from corroding utilizing sulfenyl tetrazole compound to prepare
Preparation method, specifically comprises the following steps that in the glove box (moisture ＜ 10ppm, oxygen divides ＜ 1ppm) of full argon, in proportion by line
Shape carboxylate solvent and aromatic hydrocarbon solvent mixing, useMolecular sieve, calcium hydride, lithium hydride clarification, except water, obtain organic
Solvent；At ambient temperature, in proportion lithium hexafluoro phosphate is dissolved in above-mentioned organic solvent, stirs；It is proportionally added into
Sulfenyl tetrazole compound, prepares the required electrolysis preventing box hat from corroding utilizing sulfenyl tetrazole compound to prepare
Liquid.
Above-mentioned each electrolyte is additionally operable to make the lithium ion battery preventing box hat from corroding, and this prevents the lithium ion that box hat corrodes
Battery is made up of positive electrode active materials, negative active core-shell material, barrier film and above-mentioned electrolyte；Positive electrode active materials includes answering of lithium
Close metal-oxide and formula is LiTi (PO4)5Compound, the metal composite oxide of lithium include nickel, cobalt, manganese element and
The oxide of any ratio combination；Negative active core-shell material is the hopcalite of the oxide of silicon, stannum；Barrier film is polyolefin
Perforated membrane.
The anticorrosion ability test of electrolyte
On the basis of the electrolyte described in embodiment 5, with fluorinated ethylene carbonate substituted Thio tetrazole compound, its
Remaining component is constant, and content and the preparation method of each component are the most same as in Example 5, prepares a kind of electrolyte, as a comparison case.
The lithium ion battery preventing box hat from the corroding electrolysis of embodiment 1-5 is immersed respectively after being weighed by lithium ion battery box hat
After the lithium-ion battery electrolytes of liquid and comparative example, open wide and be positioned under room temperature environment, observe after 7 hours and 100 hours lithium from
Sub-battery steel shell situation, result is as shown in table 1；After 100 hours, lithium ion battery box hat is cleaned drying to weigh, calculate lithium ion
The rate of weight loss of battery steel shell, result is as shown in table 2.
The corrosion condition of table 1 each lithium ion battery box hat
| Project | 7 hours corrosion conditions | 100 hours corrosion conditions |
| Embodiment 1 | Nothing | Slightly |
| Embodiment 2 | Nothing | Slightly |
| Embodiment 3 | Nothing | Nothing |
| Embodiment 4 | Nothing | Nothing |
| Embodiment 5 | Nothing | Nothing |
| Comparative example | Slightly | Seriously |
The weight damaed cordition of table 2 each lithium ion battery box hat
| Project | Initial weight/g | Final weight/g | Rate of weight loss/% |
| Embodiment 1 | 7.3215 | 7.3175 | 0.0546 |
| Embodiment 2 | 7.4562 | 7.4535 | 0.0362 |
| Embodiment 3 | 7.4188 | 7.4177 | 0.0148 |
| Embodiment 4 | 7.3592 | 7.3583 | 0.0122 |
| Embodiment 5 | 7.4427 | 7.4420 | 0.0094 |
| Comparative example | 7.4058 | 7.1479 | 3.4824 |
From table 1, table 2 result it will be seen that embodiment of the present invention 1-5 prevent the lithium ion battery electrolysis that box hat corrodes
Liquid is to the corrosion to box hat of the electrolyte of the corrosion comparative example to be significantly less than of box hat.It follows that the present invention's prevents box hat
The electrolyte of corrosion has the anticorrosion ability of excellence.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of the spirit or essential attributes of the present invention, it is possible to realize the present invention in other specific forms.Therefore, no matter
From the point of view of which point, all should regard embodiment as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires rather than described above limits, it is intended that all by fall in the implication of equivalency and scope of claim
Change is included in the present invention.
Although moreover, it will be appreciated that this specification is been described by according to embodiment, but the most each embodiment only wraps
Containing an independent technical scheme, this narrating mode of description is only that for clarity sake those skilled in the art should
Description can also be formed those skilled in the art through appropriately combined as an entirety, the technical scheme in each embodiment
May be appreciated other embodiments.
Claims (9)
1. utilize the electrolyte preventing box hat from corroding prepared by sulfenyl tetrazole compound, it is characterised in that according to quality hundred
Proportion by subtraction meter, is made up of organic solvent 86-90%, lithium hexafluoro phosphate 7-9% and sulfenyl tetrazole compound 3-5%；Described
Organic solvent, according to mass percent, is made up of wire carboxylate solvent 25-40% and aromatic hydrocarbon solvent 60-75%；Described
The structural formula of sulfenyl tetrazole compound as follows:
Wherein, R1-R2Selected from hydrogen, halogen, the alkyl of C1-C6 and haloalkyl thereof, the itrile group of C1-C4, the thiazolinyl of C2-C6, alcoxyl
Any one in base, carboxyl, phenyl ring, halogeno-benzene, R1-R2At least one is C1-C4 itrile group or carboxyl.
The electrolyte preventing box hat from corroding utilizing sulfenyl tetrazole compound to prepare the most according to claim 1, its
It is characterised by, according to mass percent, by organic solvent 88-90%, lithium hexafluoro phosphate 7-8% and sulfenyl tetrazole chemical combination
Thing 3-4% forms；Described organic solvent is according to mass percent, molten by wire carboxylate solvent 32-35% and aromatic hydrocarbon
Agent 65-68% forms.
The electrolyte preventing box hat from corroding utilizing sulfenyl tetrazole compound to prepare the most according to claim 2, its
It is characterised by, according to mass percent, by organic solvent 88%, lithium hexafluoro phosphate 8% and sulfenyl tetrazole compound 4%
Composition；Described organic solvent, according to mass percent, is made up of wire carboxylate solvent 32% and aromatic hydrocarbon solvent 68%.
The electrolyte preventing box hat from corroding utilizing sulfenyl tetrazole compound to prepare the most according to claim 1, its
Being characterised by, described wire carboxylate solvent is ethyl propionate, n propyl propionate, n-propyl acetate, n-butyl acetate and second
Any one or two or more mixture in acid isobutyl ester.
The electrolyte preventing box hat from corroding utilizing sulfenyl tetrazole compound to prepare the most according to claim 1, its
Being characterised by, described aromatic hydrocarbon solvent is any one in benzene, fluorobenzene, difluoro-benzene, toluene, trifluoro-benzene and dimethylbenzene
Or two or more mixture.
6. according to the arbitrary described electrolysis preventing box hat from corroding utilizing sulfenyl tetrazole compound to prepare of claim 1-5
The preparation method of liquid, it is characterised in that specifically comprise the following steps that
(1) in proportion wire carboxylate solvent and aromatic hydrocarbon solvent are mixed, useMolecular sieve, calcium hydride, lithium hydride purification remove
Miscellaneous, except water, obtain organic solvent；
(2) at ambient temperature, in proportion lithium hexafluoro phosphate is dissolved in the organic solvent of step (1), stirs；
(3) be proportionally added into sulfenyl tetrazole compound, prepare required utilize prepared by sulfenyl tetrazole compound anti-
The only electrolyte of box hat corrosion.
7. according to claim 1-5 arbitrary described electrolyte answering in terms of making the lithium ion battery preventing box hat from corroding
With, it is characterised in that the described lithium ion battery preventing box hat from corroding is by positive electrode active materials, negative active core-shell material, barrier film
And the described electrolyte preventing box hat from corroding utilizing sulfenyl tetrazole compound to prepare composition.
The electrolyte the most according to claim 7 application in terms of making the lithium ion battery preventing box hat from corroding, it is special
Levying and be, described positive electrode active materials includes that the metal composite oxide of lithium and formula are LiMx(PO4)yCompound；Described
The metal composite oxide of lithium include nickel, cobalt, manganese element and the oxide of any ratio combination thereof；Described formula is LiMx
(PO4)yCompound, M is the one in Ni, Co, Mn, Fe, Ti, V；0≤x≤5,0≤y≤5.
The electrolyte the most according to claim 7 application in terms of making the lithium ion battery preventing box hat from corroding, it is special
Levying and be, described negative active core-shell material is in lithium metal, the oxide of silicon, the oxide of stannum, crystalline carbon or agraphitic carbon
Any one or two or more mixture；Described crystalline carbon is that native graphite, graphitized coke, graphitized intermediate-phase carbon are micro-
Ballstone ink, any one or two or more mixture in graphitized intermediate-phase asphalt-based carbon fiber；Described barrier film is polyene
Hydrocarbon perforated membrane.
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| CN201610694319.8A CN106099192A (en) | 2016-08-22 | 2016-08-22 | Utilize the electrolyte preventing box hat from corroding prepared by sulfenyl tetrazole compound |
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2016
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| CN101974757A (en) * | 2010-11-04 | 2011-02-16 | 西北工业大学 | Water-soluble nickel protective agent as well as preparation method and use method thereof |
| US20130149596A1 (en) * | 2011-12-12 | 2013-06-13 | E.I Du Pont De Nemours And Company | Electrolyte solvent containing ionic liquids |
| CN104064810A (en) * | 2014-07-02 | 2014-09-24 | 东莞市凯欣电池材料有限公司 | Non-aqueous electrolyte, preparing method of non-aqueous electrolyte and lithium secondary battery |
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