CN109687010A - The high nickel electrolyte of ternary and nickelic positive lithium ion battery comprising the electrolyte - Google Patents
The high nickel electrolyte of ternary and nickelic positive lithium ion battery comprising the electrolyte Download PDFInfo
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- CN109687010A CN109687010A CN201811544531.1A CN201811544531A CN109687010A CN 109687010 A CN109687010 A CN 109687010A CN 201811544531 A CN201811544531 A CN 201811544531A CN 109687010 A CN109687010 A CN 109687010A
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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
- H01M10/0567—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
- 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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
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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
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- 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 present invention provides a kind of high nickel electrolyte of ternary and the nickelic positive lithium ion battery comprising the electrolyte, it is characterised in that: the high nickel electrolyte raw material of ternary and its weight ratio are as follows: lithium salts 13 ~ 15%, non-aqueous organic solvent 80 ~ 85%, additive 0.1 ~ 5%；Wherein, the additive is sulfuric acid vinylene, vinylene carbonate, succinonitrile, three (trimethyl silicon substrate) phosphorus, double fluorine Huang imide lis, dioxalic acid lithium borate；The lithium salts is lithium hexafluoro phosphate；The non-aqueous organic solvent is cyclic carbonate compound, dimethyl carbonate, five fluorine trimerization phosphorus eyeball of ethyoxyl；Nickelic positive lithium ion battery comprising the high nickel electrolyte of ternary, the positive diaphragm being made using the anode sizing agent of nickelic tertiary cathode powder, conductive agent, function and service binder, solvent N-methyl pyrilidone preparation, nickelic anode lithium ion battery has excellent normal-temperature circulating performance, high temperature cyclic performance and high temperature storage service life, and can substantially reduce the gas production during high temperature storage.
Description
Technical field
The invention belongs to novel energy-storing fields, are related to long circulating ternary material system electrolyte and lithium ion battery preparation skill
Art, the nickelic positive lithium ion battery more particularly to a kind of high nickel electrolyte of ternary and comprising the electrolyte.
Background technique
Currently, power lithium-ion battery wide market for electric vehicle, the ternary power battery day of high-energy density
Approval of the benefit by each depot and battery manufacturers, demand are big；To guarantee long cruising ability, ternary power battery is also continuous
Develop to nickelic direction, that is, Ni content is continuously increased in the ternary material used, and common nickelic ternary has NCM811, NCA etc..
And easily occur the sticky problem of slurry jelly in actually nickelic ternary material battery manufacturer manufacturing process, this
It is due to caused by the manufacture craft of the material.Nickelic ternary is deposited in high-temperature burning process during the manufacturing because of lithium salts
In certain volatilization, lithium salt content (general to select LiOH as lithium source, excess 0.5% ~ 1%) can be improved in ingredient, works as sintering
After the completion, a small amount of lithium salts finally remains in high-nickel material surface；Material surface residual alkali is once contacted with air, is easily adsorbed
CO in air2, H2O forms alkaline matter.In anode sizing agent configuration process, the alkaline matter on the nickelic ternary surface of major ingredient can be attacked
Binder in positive glue is hit, causes to bond dosage form double bond, generates gluing, finally cause slurry jelly, influence coating process simultaneously
Lead to battery core penalty.
In numerous application fields, more stringent requirements are proposed for cruising ability of the people to lithium ion battery, in order to improve lithium
The energy density of ion battery, it is one of effective way that developing, which has the anode material for lithium-ion batteries of height ratio capacity,.
Nickelic positive electrode due to its theoretically the specific capacity feature high compared to other positive electrodes make its become grind
Study carefully hot spot.However nickel tenor is very high so that it causes electrolyte to be easy with very strong oxidisability in nickelic positive electrode
Electrochemical oxidation reactions occur in positive electrode surface, while the variation of nickelic cathode material structure being caused to cause the transition such as nickel, cobalt golden
Belong to and reduction reaction occurs and dissolves out, so as to cause the deterioration of lithium ion battery chemical property.Therefore, develop it is a kind of with it is nickelic just
The electrolyte that pole material matches is very crucial.
Summary of the invention
The problem to be solved in the present invention is to cause anode sizing agent jelly to follow in existing nickelic ternary material battery production process
The series such as deterioration of battery core penalty and battery performance caused by strong oxidizing property are asked in ring, nickelic positive electrode
Topic provides a kind of high nickel electrolyte of ternary and the nickelic positive lithium ion battery comprising the electrolyte, includes the high nickel electrowinning of ternary
The nickelic positive lithium ion battery of liquid has excellent normal-temperature circulating performance, high temperature cyclic performance and high temperature storage service life, and can
To substantially reduce the gas production during high temperature storage.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of high nickel electrolyte of ternary, feature exist
In: it is as follows including raw material and its weight ratio: lithium salts 13 ~ 15%, non-aqueous organic solvent 80 ~ 85%, additive 0.1 ~ 5%；
Wherein, non-aqueous organic solvent is cyclic carbonate compound EC, dimethyl carbonate DMC, five fluorine trimerization phosphorus eyeball FPN of ethyoxyl
Weight ratio in the electrolytic solution is respectively 15 ~ 20%；
The additive be sulfuric acid vinylene DTD, vinylene carbonate VC, succinonitrile SN, three (trimethyl silicon substrate) phosphorus TMSP,
Double fluorine Huang imide li LiFSI, dioxalic acid lithium borate LiBOB.
Preferably, the sulfuric acid vinylene DTD, vinylene carbonate VC, succinonitrile SN, three (trimethyl silicon substrate) phosphorus
The weight ratio of TMSP in the electrolytic solution is respectively 1 ~ 5%；Double fluorine Huang imide li LiFSI, dioxalic acid lithium borate LiBOB are
The weight ratio of additive lithium salts in the electrolytic solution is respectively 0.1 ~ 0.5%
Preferably, the lithium salts is lithium hexafluoro phosphate LiPF6.
Preferably, the additive is sulfuric acid vinylene DTD, vinylene carbonate VC, succinonitrile SN, three (front threes
Base silicon substrate) two or more in phosphorus TMSP.
Preferably, the non-aqueous organic solvent is cyclic carbonate compound EC, dimethyl carbonate DMC, ethyoxyl five
At least one of fluorine trimerization phosphorus eyeball FPN.
A kind of nickelic positive lithium ion battery, it is characterised in that: the battery includes the high nickel electrolyte of the ternary, further includes
The positive diaphragm being made is coated using anode sizing agent, coats the cathode membrane being made, isolation film using negative electrode slurry；
Wherein, the anode sizing agent is nickelic ternary Li-ion positive electrode slurry, and component is as follows by weight ratio:
Nickelic tertiary cathode powder 90% ~ 98%
Conductive agent 1% ~ 5%
Function and service binder 1% ~ 5%
It further include solvent N-methyl pyrilidone；The usage amount of the solvent N-methyl pyrilidone guarantees the solid of anode sizing agent
Content of material is 60% ~ 80%.
Preferably, the function and service binder is the fluorine resins, styrene butadiene copolymers such as Kynoar
The one or more of object, acrylic acid series copolymer etc..
Preferably, the function and service binder is A class high molecular weight alkali resistance binder PVDF and B class low molecular weight
High bond strength binder PVDF；Wherein, A type alkali-resistant binder and B class high bond strength weight of binder ratio are 1:2 ~ 4.
A kind of preparation method of nickelic positive lithium ion battery, processing step are as follows:
1) preparation of the high nickel electrolyte of ternary
A) non-aqueous organic solvent cyclic carbonate compound EC, dimethyl carbonate DMC, five fluorine trimerization phosphorus eyeball FPN of ethyoxyl are pressed
Weight proportion is sequentially injected into mixer respectively, while starting blender and cooling system, organic solvent -10 ~ 10 DEG C freeze 25 ~
30 minutes, cooling, stirring was sufficiently mixed；
B) lithium salts lithium hexafluoro phosphate LiPF6 is sufficiently mixed dissolution, reaction by weight cooling, stirring in mixer is added；It will
Additive sulfuric acid vinylene DTD, vinylene carbonate VC, succinonitrile SN, three (trimethyl silicon substrate) phosphorus TMSP, double fluorine Huang acyls are sub-
Amine lithium LiFSI, dioxalic acid lithium borate LiBOB by weight ratio respectively sequence be added cooling, stirring in mixer be sufficiently mixed it is molten
Solution, reaction, 1 ~ 2h of mixing, are configured to the high nickel electrolyte of ternary；
2) anode sizing agent and positive diaphragm and preparation
A) by A class, B class binder is added in solvent N-methyl pyrilidone by weight, prepare glue；
B) by conductive agent, nickelic ternary material is added in glue together by weight, and opens vacuum high-speed stirred, until dispersion
Slurry configuration to be completed after uniformly, controls the temperature of glue and slurry at 25 ~ 50 DEG C, the final viscosity for controlling slurry is 5000 ~
5600mPa.s；
C) anode sizing agent is coated in the positive diaphragm that coated, drying is made on plus plate current-collecting body.
The advantages and positive effects of the present invention are:
1, the high nickel electrolyte of ternary of the present invention uses lithium salts LiPF6, organic solvent, additive and difluoro lithium borate and double fluorine Huang acyls
Imines salt additives lithium salts, double fluorine Huang imide li LiFSI can keep thermostabilization to 180 DEG C, and in the carbonic acid of low-k
Solubility with higher in esters solvent；Compared to LiPF6 system, the carbonic ester electrolyte of LiFSI has at ~ 50 ~ 50 DEG C
There is higher conductivity, the lithium transport number of the system is up to 0.5 ~ 0.6 at room temperature, so that battery be enable preferably to be recycled
Efficiency；Inhibit the pyrolytic of LiPF6 simultaneously, LiBOB good film-forming property, low temperature performance well have fine compatibility with anode；
One layer of passivating film can be formed on Al foil surface, and inhibit electrolyte oxidation；LiFSI conductivity is high, water-sensitive sensitivity is low and thermostabilization
Property is good, and the decomposition of LiPF6 can be effectively suppressed in the addition of two additive lithium salts, and the cycle performance of Lai Tisheng electrolyte uses this
The lithium ion battery of electrolyte has excellent normal-temperature circulating performance, high temperature cyclic performance and high temperature storage service life, and can show
Write the gas production reduced during high temperature storage.
2, the high nickel electrolyte of ternary of the present invention uses in lithium salt electrolyte and is mixed into additive, sulfuric acid vinylene DTD, carbonic acid
Vinylene VC, succinonitrile SN, three (trimethyl silicon substrate) phosphorus TMSP and double fluorine Huang imide li LiFSI, dioxalic acid lithium borate
Synergistic effect is generated in LiBOB combination addition electrolyte, lithium electrode is formed on its surface non-ordinary light under higher discharge rate
Sliding, even compact SEI film, is individually added into additive three (trimethyl silicon substrate) phosphorus compound in the electrolytic solution, can improve lithium
The high temperature cyclic performance of ion battery and high temperature storage service life, three (trimethyl silicon substrate) phosphorus compounds significantly reduce the interface of anode
Impedance is conducive to lithium ion and moves in positive interface gan, significantly reduces nickelic positive electrode to the oxidation activity of electrolyte,
Especially its oxidation to electrolyte under the high temperature conditions, caused by the variation because of nickelic cathode material structure can be inhibited
The transition metal such as nickel, cobalt occur reduction reaction and dissolve out, and improve high temperature cyclic performance and the high temperature storage service life of lithium ion battery.
3, the high nickel electrolyte of ternary of the present invention, due to being subtracted using electrode polarization degree after additive sulfuric acid vinylene DTD
It is small, to form stable SEI film in electrode surface, the resistance of electrode process Li migration is reduced, being conducive to can removal lithium embedded mistake
The progress of journey improves battery and is continuously circulated ability under charge-discharge magnification, and (trimethyl silicon substrate) the phosphorus TMSP of additive three is used for Li/
Graphite cell improves its cyclical stability and for the first time coulombic efficiency；Meanwhile adding non-aqueous organic solvent vinylene carbonate VC
The cycle performance index of three (trimethyl silicon substrate) phosphorus TMSP is significantly improved, so that the long circulating performance of battery is improved, up to 3000
Secondary above circulation volume holding Shuai≤80% or more.
4, the anode sizing agent of the nickelic positive lithium ion battery of the present invention uses nickelic tertiary cathode powder, conductive agent, anode
Function and service binder and solvent N-methyl pyrilidone are prepared, since there are residual alkali Li for nickelic ternary powder body material surface2CO3,
LiOH etc., free alkali can attack C ~ F/C on binder ~ H key when configuring anode sizing agent, cause binder to take off HF and form double bond,
It is crosslinked, ultimately forming jelly can not be coated with, and select this function and service binder, the fluorine resins such as Kynoar are selected,
Styrene-butadiene copolymer, one or more, the alkali resistance binder A class and high bond strength of acrylic acid series copolymer etc.
Binder B class avoids pulping process from not occurring jelly and guarantees that final coated product adhesion strength is up to standard, the good slurry of slurry fluidity
There is foil adhesion strength good, ensure that the performance of subsequent battery core.
Detailed description of the invention
Fig. 1 is the curve graph of the nickelic positive lithium ion battery difference conservation rate discharge capacity of the present invention as schemed.
Specific embodiment
Below in conjunction with embodiment and attached drawing, the present invention is described in further detail.
Referring to Fig. 1, the present invention provides a kind of high nickel electrolyte of ternary and the nickelic positive lithium-ion electric comprising the electrolyte
Pond.
Embodiment one:
The high nickel electrolyte of 1 ternary of table is prepared according to raw material and weight ratio, configuration proportion is counted as unit of the every KG of weight ratio
It calculates and prepares (this formula is only limitted to cylindrical body series lithium ion battery):
| Electrolyte | LiPF6 | LIFSI | LiBOB | TMSP | FPN | SN | EC | DMC | FEC | DTD | VC |
| Implement one | 150 | 2 | 3 | 3 | 10 | 15 | 175 | 554 | 70 | 15 | 3 |
| Implement two | 150 | 2 | 3 | 5 | 10 | 15 | 175 | 552 | 70 | 15 | 3 |
| Implement three | 150 | 2 | 5 | 3 | 10 | 15 | 175 | 552 | 70 | 15 | 3 |
First group: the preparation of the high nickel electrolyte of ternary
1) preparation of the high nickel electrolyte of ternary
A) non-aqueous organic solvent cyclic carbonate compound EC, dimethyl carbonate DMC, five fluorine trimerization phosphorus eyeball FPN of ethyoxyl are pressed
Weight proportion EC:175g, DMC:554g, FPN:10g are sequentially injected into mixer respectively, while starting blender and cooling system,
Organic solvent freezes 25 ~ 30 minutes at -10 ~ 10 DEG C, and cooling, stirring is sufficiently mixed；
B) lithium salts lithium hexafluoro phosphate LiPF6 is sufficiently mixed by weight cooling, stirring in LiPF6:150g addition mixer molten
Solution, reaction；By additive sulfuric acid vinylene DTD, vinylene carbonate VC, succinonitrile SN, three (trimethyl silicon substrate) phosphorus TMSP,
Double fluorine Huang imide li LiFSI, dioxalic acid lithium borate LiBOB DTD:15g, VC:3g, SN:15g, TMSP:3g by weight ratio,
Cooling, stirring in mixer is sequentially added respectively and is sufficiently mixed dissolution, reaction, 1 ~ 2h of mixing by LIFSI:2g, LiBOB:3g, prepares
At the high nickel electrolyte of ternary, after detection is qualified, the filling weighing storage of product.
Second group: the preparation of the high nickel electrolyte of ternary
A) non-aqueous organic solvent cyclic carbonate compound EC, dimethyl carbonate DMC, five fluorine trimerization phosphorus eyeball FPN of ethyoxyl are pressed
Weight proportion EC:175g, DMC:552g, FPN:10g are sequentially injected into mixer respectively, while starting blender and cooling system,
Organic solvent freezes 25 ~ 30 minutes at -10 ~ 10 DEG C, and cooling, stirring is sufficiently mixed；
B) lithium salts lithium hexafluoro phosphate LiPF6 is sufficiently mixed by weight cooling, stirring in LiPF6:150g addition mixer molten
Solution, reaction；By additive sulfuric acid vinylene DTD, vinylene carbonate VC, succinonitrile SN, three (trimethyl silicon substrate) phosphorus TMSP,
Double fluorine Huang imide li LiFSI, dioxalic acid lithium borate LiBOB DTD:15g, VC:3g, SN:15g, TMSP:5g by weight ratio,
Cooling, stirring in mixer is sequentially added respectively and is sufficiently mixed dissolution, reaction, 1 ~ 2h of mixing by LIFSI:2g, LiBOB:3g, prepares
At the high nickel electrolyte of ternary, after detection is qualified, the filling weighing storage of product.
Third group: the preparation of the high nickel electrolyte of ternary
A) non-aqueous organic solvent cyclic carbonate compound EC, dimethyl carbonate DMC, five fluorine trimerization phosphorus eyeball FPN of ethyoxyl are pressed
Weight proportion EC:175g, DMC:552g, FPN:10g are sequentially injected into mixer respectively, while starting blender and cooling system,
Organic solvent freezes 25 ~ 30 minutes at -10 ~ 10 DEG C, and cooling, stirring is sufficiently mixed；
B) lithium salts lithium hexafluoro phosphate LiPF6 is sufficiently mixed by weight cooling, stirring in LiPF6:150g addition mixer molten
Solution, reaction；By additive sulfuric acid vinylene DTD, vinylene carbonate VC, succinonitrile SN, three (trimethyl silicon substrate) phosphorus TMSP,
Double fluorine Huang imide li LiFSI, dioxalic acid lithium borate LiBOB DTD:15g, VC:3g, SN:15g, TMSP:5g by weight ratio,
Cooling, stirring in mixer is sequentially added respectively and is sufficiently mixed dissolution, reaction, 1 ~ 2h of mixing by LIFSI:5g, LiBOB:3g, prepares
At the high nickel electrolyte of ternary, after detection is qualified, the filling weighing storage of product.
In embodiment, the nickelic electrolysis additive cyclic carbonate compound EC of ternary, selected from the knot of chemistry shown in Formulas I
At least one of the compound of structure formula, compound with chemical structural formula shown in formula n.
Be individually added into lithium-ion battery electrolytes or three (trimethyl silicon substrate) phosphorus compound TMSP, can improve lithium from
The high temperature cyclic performance of sub- battery and high temperature storage service life.Three (trimethyl silicon substrate) phosphorus compound TMSP N atom containing there are three, often
Having N atom respectively has a pair of of lone pair electrons, can effectively be complexed with high-valency metal atom Ni, Co, Mn etc., anode can be significantly reduced
Interface impedance, be conducive to lithium ion and moved in positive interface gan, and N atom and high-valency metal atom Ni, Co, Mn etc.
Complexing significantly reduce nickelic positive electrode under the oxidation activity of electrolyte, especially hot conditions its to electrolyte
Oxidation may further inhibit the transition metal such as nickel, the cobalt caused by the variation because of nickelic cathode material structure that reduction occurs anti-
It answers and dissolves out, high temperature cyclic performance and high temperature storage service life so as to improve lithium ion battery；On the other hand, three (trimethyl silicane
Base) phosphorus compound easily cathode interface occur electrochemical reducting reaction generate the biggish solid electrolyte interface film SEI of impedance ratio
Film is unfavorable for lithium ion and moves in negative electrode material Biao Mian gan, to deteriorate the normal-temperature circulating performance of lithium ion battery；Three (front threes
Base silicon substrate) weight ratio of the phosphorus compound TMSP in nonaqueous electrolytic solution be 1 ~ 3%, as three (trimethyl silicon substrate) phosphorus compound TMSP
Chelation structure when weight ratio in nonaqueous electrolytic solution is lower than 1%, with transition metal element formation in positive electrode active materials
It is not fine and close enough, can not effectively inhibit the oxidation reaction between nonaqueous electrolytic solution and positive electrode active materials, thus be unable to improve lithium from
The high-temperature storage performance and high temperature cyclic performance of sub- battery；When quality percentage of the isocyanurate compound in nonaqueous electrolytic solution
Content it is high 3% when, in positive electrode active materials transition metal element formed complexing layer it is blocked up, cause positive impedance significant
Increase, the cycle performance that will lead to lithium ion battery is deteriorated.
Meanwhile the double fluorine Huang imide li LiFSI of additive lithium salts can keep thermostabilization to 180 DEG C, and in low-k
Carbonate-based solvent in solubility with higher, the carbonic ester electrolyte of double fluorine Huang imide li LiFSI is at -50 ~ 50 DEG C
Higher conductivity is all had, the lithium transport number of the system is up to 0.5 ~ 0.6 at room temperature, so that battery be enable to obtain preferably
Cycle efficieny, while inhibiting the pyrolytic of lithium hexafluoro phosphate LiPF6, dioxalic acid lithium borate LiBOB good film-forming property, cryogenic property
It is good, there is fine compatibility with anode；One layer of passivating film can be formed on Al foil surface, and inhibit electrolyte oxidation.Double fluorine are yellow
Imide li LiFSI conductivity is high, water-sensitive sensitivity is low and thermal stability is good, and hexafluorophosphoric acid can be effectively suppressed in the addition of two lithium salts
The decomposition of lithium LiPF6, the cycle performance of Lai Tisheng electrolyte.
Embodiment two:
A kind of nickelic positive lithium ion battery, is included the high nickel electrolyte of ternary, the cathode film being made is coated using anode sizing agent
Piece coats the cathode membrane being made, isolation film using negative electrode slurry；
First group: nickelic tertiary cathode slurry preparation, nickelic anode ternary powder 92%, conductive agent 2%, function and service binder
2%, wherein A type alkali-resistant binder PVDF:B class high bond strength binder PVDF=1:2 in complex function binder；It is wherein high
The chemical molecular formula of nickel tertiary cathode are as follows: LiNixCoyMzO2, wherein x+y+z=1,0.6≤x < 1, M can represent Mn, Al or other
Metallic element.
Solvent is N-Methyl pyrrolidone, and usage amount guarantees the solid matter content of slurry 65%.
The preparation of above-mentioned nickelic tertiary cathode slurry: 1) by A class, B class binder is added to Solvents N-methyl by weight
In pyrrolidones, prepare glue；2) by conductive agent, nickelic ternary material is added in glue together, and opens vacuum high-speed stirring
It mixes, until completing slurry configuration after being uniformly dispersed.The temperature of glue and slurry is controlled in whole process at 30 DEG C, final control is starched
The viscosity of material is 5600mPa.s；Anode sizing agent is coated in the positive diaphragm that coated, drying is made on plus plate current-collecting body.
Second group: nickelic tertiary cathode slurry preparation, nickelic anode ternary powder 95%, conductive agent 3%, function and service bonding
Agent 4%, wherein A type alkali-resistant binder in complex function binder: B class high bond strength binder=1:3；Wherein nickelic ternary
The chemical molecular formula of anode are as follows: LiNixCoyMzO2, wherein x+y+z=1,0.6≤x < 1, M can represent Mn, Al or other metals member
Element.
Solvent is N-Methyl pyrrolidone, and usage amount guarantees the solid matter content of slurry 74%.
The preparation of above-mentioned nickelic tertiary cathode slurry: 1) by A class, B class binder is added in full amount solvent by calculated weight
In N-Methyl pyrrolidone, prepare glue.2) by conductive agent, nickelic ternary material is added in glue together, and opens vacuum
High-speed stirred, until completing slurry configuration after being uniformly dispersed.The temperature of glue and slurry is controlled in whole process at 40 DEG C, finally
The viscosity for controlling slurry is 6400mPa.s；Anode sizing agent is coated in the anode that coated, drying is made on plus plate current-collecting body
Diaphragm.
Third group: nickelic tertiary cathode slurry configuration, nickelic anode ternary powder 98%, conductive agent 5%, function and service bonding
Agent 5%；Wherein A type alkali-resistant binder in complex function binder: B class high bond strength binder=1:4；Wherein nickelic ternary
The chemical molecular formula of anode are as follows: LiNixCoyMzO2, wherein x+y+z=1,0.6≤x < 1, M can represent Mn, Al or other metals member
Element.
Solvent is N-Methyl pyrrolidone, and usage amount guarantees the solid matter content of slurry 80%.
The preparation of above-mentioned nickelic tertiary cathode slurry: 1) by A class, B class binder is added in full amount solvent by calculated weight
In N-Methyl pyrrolidone, prepare glue.2) by conductive agent, nickelic ternary material is added in glue together, and opens vacuum
High-speed stirred, until completing slurry configuration after being uniformly dispersed.The temperature of glue and slurry is controlled in whole process at 45 DEG C, finally
The viscosity for controlling slurry is 5000mPa.s；Anode sizing agent is coated in the anode that coated, drying is made on plus plate current-collecting body
Diaphragm.
The cycle charge-discharge system of nickelic anode lithium ion battery are as follows:
1. test temperature: 25 DEG C ± 3 DEG C；
2. charging modes: using 1100mAh (0.5C) constant-current constant-voltage charging to 4.2V, cut-off current 0.05C (mA)；
3. discharge mode: using 1100mAh (0.5C) constant-current discharge to 3.0V；
4. cycle-index: repeating above-mentioned circulation system 3000 weeks, Rong amount holding Shuai≤80% or more.
The curve graph of different conservation rate discharge capacities is as shown in Figure 1；Wherein horizontal axis is cycle-index, and the longitudinal axis is to keep
Rate.
Reduce from circulation the results show that introducing electrode polarization degree after 1.5% sulfuric acid vinylene DTD, thus in electrode table
Face forms stable SEI film, reduce electrode process Li migration resistance, be conducive to can removal lithium embedded process progress, improve electricity
Pond is continuously circulated ability under charge-discharge magnification, and three (trimethyl silicon substrate) phosphorus TMSP additives are improved for Li/ graphite cell
Its cyclical stability and for the first time coulombic efficiency；The coulombic efficiency for adding VC is 92.9%, and slightly lower coulombic efficiency is attributed to the electricity of VC
Electronation, and the coulombic efficiency for adding 3.0% 3 (trimethyl silicon substrate) phosphorus TMSP is up to 95.2%.For cycle performance, following
After ring 2000 encloses, 2.0% 3 (trimethyl silicon substrate) phosphorus TMSP of addition is 96.8%；Phosphorus TMSP high is for the first time for three (trimethyl silicon substrates)
Coulombic efficiency can mitigate the amount of positive electrode in LIBs, to improve the long circulating performance of battery.
The embodiments of the present invention have been described in detail above, but content is only the preferred embodiment of the present invention,
It should not be considered as limiting the scope of the invention.All changes and improvements made in accordance with the scope of the present invention are same,
It should still belong within this patent covering scope.
Claims (9)
1. a kind of high nickel electrolyte of ternary, it is characterised in that: as follows including raw material and its weight ratio: lithium salts 13 ~ 15% non-aqueous has
Solvent 80 ~ 85%, additive 0.1 ~ 5%；
Wherein, the non-aqueous organic solvent is cyclic carbonate compound EC, dimethyl carbonate DMC, five fluorine trimerization phosphorus of ethyoxyl
The weight ratio of eyeball FPN in the electrolytic solution is respectively 15 ~ 20%；
The additive be sulfuric acid vinylene DTD, vinylene carbonate VC, succinonitrile SN, three (trimethyl silicon substrate) phosphorus TMSP,
Double fluorine Huang imide li LiFSI, dioxalic acid lithium borate LiBOB.
2. the high nickel electrolyte of a kind of ternary according to claim 1, it is characterised in that: the sulfuric acid vinylene DTD, carbon
Sour vinylene VC, succinonitrile SN, three weight ratios of (trimethyl silicon substrate) phosphorus TMSP in the electrolytic solution are respectively 1 ~ 5%；It is described double
Fluorine Huang imide li LiFSI, dioxalic acid lithium borate LiBOB be the weight ratio of additive lithium salts in the electrolytic solution be respectively 0.1 ~
0.5%。
3. the high nickel electrolyte of a kind of ternary according to claim 1, it is characterised in that: the lithium salts is lithium hexafluoro phosphate
LiPF6。
4. the high nickel electrolyte of a kind of ternary according to claim 1, it is characterised in that: the additive is sulfuric acid Asia ethylene
Ester DTD, vinylene carbonate VC, succinonitrile SN, two or more in three (trimethyl silicon substrate) phosphorus TMSP.
5. the high nickel electrolyte of a kind of ternary according to claim 1, it is characterised in that: the non-aqueous organic solvent is ring-type
At least one of carbonate products EC, dimethyl carbonate DMC, five fluorine trimerization phosphorus eyeball FPN of ethyoxyl.
6. a kind of nickelic positive lithium ion battery, it is characterised in that: the battery includes the high nickel electrolyte of the ternary, further includes making
The positive diaphragm being made is coated with anode sizing agent, coats the cathode membrane being made, isolation film using negative electrode slurry；
Wherein, the anode sizing agent is nickelic ternary Li-ion positive electrode slurry, and component is as follows by weight ratio:
Nickelic tertiary cathode powder 90% ~ 98%
Conductive agent 1% ~ 5%
Function and service binder 1% ~ 5%
It further include solvent N-methyl pyrilidone；The usage amount of the solvent N-methyl pyrilidone guarantees the solid of anode sizing agent
Content of material is 60% ~ 80%.
7. the nickelic positive lithium ion battery of one kind according to claim 6, it is characterised in that: the function and service binder
For the one or more of the fluorine resins such as Kynoar, styrene-butadiene copolymer, acrylic acid series copolymer etc..
8. the nickelic positive lithium ion battery of one kind according to claim 6, it is characterised in that: the function and service binder
For A class high molecular weight alkali resistance binder PVDF and B class low molecular weight high bond strength binder PVDF；Wherein, A class is alkaline-resisting
Property binder and B class high bond strength weight of binder ratio be 1:2 ~ 4.
9. a kind of preparation method of nickelic positive lithium ion battery, processing step are as follows according to claim 6:
1) preparation of the high nickel electrolyte of ternary
A) non-aqueous organic solvent cyclic carbonate compound EC, dimethyl carbonate DMC, five fluorine trimerization phosphorus eyeball FPN of ethyoxyl are pressed
Weight proportion is sequentially injected into mixer respectively, while starting blender and cooling system, organic solvent -10 ~ 10 DEG C freeze 25 ~
30 minutes, cooling, stirring was sufficiently mixed；
B) lithium salts lithium hexafluoro phosphate LiPF6 is sufficiently mixed dissolution, reaction by weight cooling, stirring in mixer is added；It will
Additive sulfuric acid vinylene DTD, vinylene carbonate VC, succinonitrile SN, three (trimethyl silicon substrate) phosphorus TMSP, double fluorine Huang acyls are sub-
Amine lithium LiFSI, dioxalic acid lithium borate LiBOB by weight ratio respectively sequence be added cooling, stirring in mixer be sufficiently mixed it is molten
Solution, reaction, 1 ~ 2h of mixing, are configured to the high nickel electrolyte of ternary；
2) anode sizing agent and positive diaphragm and preparation
A) by A class, B class binder is added in solvent N-methyl pyrilidone by weight, prepare glue；
B) by conductive agent, nickelic ternary material is added in glue together by weight, and opens vacuum high-speed stirred, until dispersion
Slurry configuration to be completed after uniformly, controls the temperature of glue and slurry at 25 ~ 50 DEG C, the final viscosity for controlling slurry is 5000 ~
5600mPa.s；
C) anode sizing agent is coated in the positive diaphragm that coated, drying is made on plus plate current-collecting body.
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