CN103682354B - A kind of all-solid lithium-ion battery compound electrode material and preparation method thereof and all-solid lithium-ion battery - Google Patents

A kind of all-solid lithium-ion battery compound electrode material and preparation method thereof and all-solid lithium-ion battery Download PDF

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CN103682354B
CN103682354B CN201210345669.5A CN201210345669A CN103682354B CN 103682354 B CN103682354 B CN 103682354B CN 201210345669 A CN201210345669 A CN 201210345669A CN 103682354 B CN103682354 B CN 103682354B
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ion battery
polymer monomer
solid lithium
lithium
electrode active
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CN103682354A (en
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裴佳宁
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Huawei Technologies 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/62—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

Embodiments provide a kind of all-solid lithium-ion battery compound electrode material, including electrode active material and the clad being arranged on described electrode active material surface, the material of clad is counted by weight and is included: polymer, 0.1 ~ 10 part of lithium salts, 0.1 ~ 10 part of polymerization initiator and 50 ~ 99.9 parts of plasticizers that 0.1 ~ 20 part of polymer monomer and 0.1 ~ 50 part of ethylene glycol derivative are formed, one or more in fluorine-based polymer monomer, ether polymer monomer, acrylic polymer monomer and acrylonitrile polymers monomer of polymer monomer.Clad can effectively suppress the formation of space charge layer, contributes to reducing all-solid lithium-ion battery interface resistance, thus improves cyclical stability and the durability of all-solid-state battery.The embodiment of the present invention additionally provides the preparation method of this all-solid lithium-ion battery compound electrode material, comprises the all-solid lithium-ion battery of this compound electrode material.

Description

A kind of all-solid lithium-ion battery compound electrode material and preparation method thereof and all-solid lithium-ion battery
Technical field
The present invention relates to field of lithium ion battery, particularly relate to a kind of compound electricity of all-solid lithium-ion battery Pole material and preparation method thereof and all-solid lithium-ion battery.
Background technology
From last century the nineties, in numerous energy substitution products, lithium ion battery is with higher energy The features such as density, good cycle performance, memory-less effect are paid close attention to by people.
In recent years, along with electric motor car and the increase of large-scale fixation equipment electric power storage purposes battery applications demand, there is peace Complete and long-life all-solid lithium-ion battery starts to be attracted attention, and it uses the solid inorganic conduct do not fired Electrolyte, not only has a higher energy density, and has good security and stability, erecting device simultaneously Simply, the advantage such as low cost of manufacture.
It is relevant that the inorganic solid electrolyte currently mainly studied and apply has focused largely on Oxide and sulfide Material, compared with oxide, sulfide is owing to having the good characteristics such as stronger ionic conductivity by researcher Favor.But, there is a common problem in the application in sulfide solid electrolyte, Gu i.e. electrode/ State electrolyte interface, has the sulfide solid electrolyte of crosslinking chalcogen representated by sulfur easily and electrode active Property material reaction and decompose, thus form space charge layer, make the interface shape between electrode/solid electrolyte The high impedance that in pairs lithium ion moves, causes battery to have a relatively low output, relatively low durability and following Ring performance.
Summary of the invention
In consideration of it, embodiment of the present invention first aspect provides a kind of all-solid lithium-ion battery compound electrode material Material, decomposes to solve easy the reaction with electrode active material of sulfide solid electrolyte, thus forms space electricity Lotus layer, makes the interface between electrode/solid electrolyte form the high impedance moving lithium ion, causes battery There is relatively low output, relatively low durability and the problem of cycle performance.Embodiment of the present invention second party Face provides the preparation method of a kind of all-solid lithium-ion battery compound electrode material.The embodiment of the present invention Three aspects provide a kind of all-solid lithium-ion battery.
First aspect, embodiments provides a kind of all-solid lithium-ion battery compound electrode material, bag Include electrode active material and be arranged on the clad on described electrode active material surface, described electrode active material For positive electrode active materials or negative active core-shell material, the material of described clad is counted by weight and is included: 0.1 ~ 20 The polymer of part polymer monomer and 0.1 ~ 50 part of ethylene glycol derivative formation, 0.1 ~ 10 part of lithium salts, 0.1 ~ 10 Part polymerization initiator and 50 ~ 99.9 parts of plasticizers, described polymer monomer is selected from fluorine-based polymer monomer, ethers One or more in polymer monomer, acrylic polymer monomer and acrylonitrile polymers monomer.
Compared with prior art, the all-solid lithium-ion battery compound electrode material that the present invention provides has cladding Layer, described clad is coated on described electrode active material surface as interface-modifying layer, and not with electrode Active material and solid electrolyte react.The present invention is coated on the clad on electrode active material surface, In all-solid lithium-ion battery, as electrode active material and the intermediate layer of solid electrolyte, can effectively press down Sulfide solid electrolyte S processed3P-S-SP3Crosslinking sulfur in division center and electrode active material react and Decompose, the formation of suppression space charge layer, suppress the formation of high interface impedance, from without reducing lithium ion Conductivity.All-solid lithium-ion battery compound electrode material finally can make battery have higher output work Rate, has good durability and stable circulation performance.
Preferably, described fluorine-based polymer monomer is vinylidene and/or biasfluoroethylene-hexafluoropropylene, and ethers gathers Monomer adduct is oxirane and/or expoxy propane, and acrylic polymer monomer is methyl methacrylate.
Preferably, described ethylene glycol derivative is selected from ethylene glycol methacrylate, ethylene glycol dimethyl propylene One or more in acid esters, EDIA and glycol diacrylate.
Preferably, lithium salts is selected from lithium perchlorate LiClO4, LiBF4 LiBF4, lithium hexafluoro phosphate LiPF6、 Hexafluoroarsenate lithium LiAsF6, trifluoromethyl sulfonic acid lithium LiCF3SO3With bis trifluoromethyl sulphonyl lithamide LiN(CF3SO2)2In one or more.
Preferably, polymerization initiator is selected from azodiisobutyronitrile, benzoyl peroxide, acetyl peroxide and hexichol One or more in ketone.
Preferably, plasticizer selected from Allyl carbonate, dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate and One or more in ethylene carbonate.
Preferably, the material of described clad also includes the additive of 0.1 ~ 30 part, and described additive is selected from receiving Rice SiO2, nano-TiO2, nanometer Al2O3, single-layer carbon nano-tube, multilayer carbon nanotube, zeolite, montmorillonite With one or more in molecular sieve ZSM-5.
Preferably, positive electrode active materials is selected from cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, nickel cobalt mangaic acid One or more in lithium, vanadic anhydride, molybdenum trioxide and titanium disulfide.
Preferably, negative active core-shell material is selected from graphite, hard carbon, silicon, silicon oxide compound, ashbury metal, lithium cobalt nitrogen One or more in compound, lithium metal and lithium alloy.
Preferably, the thickness of clad is 0.1 ~ 2000nm.It is highly preferred that the thickness of clad is 0.1~1000nm。
Preferably, described clad does not contains electrode active material away from the side of electrode active material.
A kind of all-solid lithium-ion battery compound electrode material that embodiment of the present invention first aspect provides, can be very Effectively suppression sulfide solid electrolyte S3P-S-SP3Crosslinking sulfur in division center occurs with electrode active material React and decompose, the formation of suppression space charge layer, suppresses the formation of high interface impedance, from without reducing The conductivity of lithium ion；Additionally, described clad will not hinder lithium ion at electrode active material and solid-state electricity Solve the conduction between matter；Therefore, all-solid lithium-ion battery compound electrode material finally can make battery have Higher output, has good durability and cycle performance.
Second aspect, embodiments provides the system of a kind of all-solid lithium-ion battery compound electrode material Preparation Method, comprises the following steps:
Count by weight, 0.1 ~ 20 part of polymer monomer, 0.1 ~ 50 part of ethylene glycol derivative, 0.1 ~ 10 part Lithium salts, 0.1 ~ 10 part of polymerization initiator and 50 ~ 99.9 parts of plasticizers, preparation obtains mixed solution, described polymerization Thing monomer is selected from fluorine-based polymer monomer, ether polymer monomer, acrylic polymer monomer and acrylonitrile One or more in base polymer monomer；
Described mixed solution is arranged on by method of electrostatic spinning, electro-blown spinning method, liquid phase spraying process or print process Electrode active material surface, described electrode active material is positive electrode active materials or negative active core-shell material, subsequently Raw at described electrode active material surface aggregate by thermal polymerization, electron beam polymerization method or ultraviolet polymerization Become clad, prepare all-solid lithium-ion battery compound electrode material.
Preferably, described fluorine-based polymer monomer is vinylidene and/or biasfluoroethylene-hexafluoropropylene, and ethers gathers Monomer adduct is oxirane and/or expoxy propane, and acrylic polymer monomer is methyl methacrylate.
Preferably, described ethylene glycol derivative is selected from ethylene glycol methacrylate, ethylene glycol dimethyl propylene One or more in acid esters, EDIA and glycol diacrylate.
Preferably, lithium salts is selected from lithium perchlorate LiClO4, LiBF4 LiBF4, lithium hexafluoro phosphate LiPF6、 Hexafluoroarsenate lithium LiAsF6, trifluoromethyl sulfonic acid lithium LiCF3SO3With bis trifluoromethyl sulphonyl lithamide LiN(CF3SO2)2In one or more.
Preferably, polymerization initiator is selected from azodiisobutyronitrile, benzoyl peroxide, acetyl peroxide and hexichol One or more in ketone.
Preferably, plasticizer selected from Allyl carbonate, dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate and One or more in ethylene carbonate.
Preferably, during described preparation mixed solution, also include the additive adding 0.1 ~ 30 part, described Additive is selected from Nano-meter SiO_22, nano-TiO2, nanometer Al2O3, single-layer carbon nano-tube, multilayer carbon nanotube, One or more in zeolite, montmorillonite and molecular sieve ZSM-5.
Preferably, positive electrode active materials is selected from cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, nickel cobalt mangaic acid One or more in lithium, vanadic anhydride, molybdenum trioxide and titanium disulfide.
Preferably, negative active core-shell material is selected from graphite, hard carbon, silicon, silicon oxide compound, ashbury metal, lithium cobalt nitrogen One or more in compound, lithium metal and lithium alloy.
Preferably, the thickness of clad is 0.1 ~ 2000nm.It is highly preferred that the thickness of clad is 0.1~1000nm。
Preferably, described clad does not contains electrode active material away from the side of electrode active material.
The system of a kind of all-solid lithium-ion battery compound electrode material that embodiment of the present invention second aspect provides Preparation Method is simple, and the all-solid lithium-ion battery compound electrode material prepared can improve electrode/solid-state electricity Solve matter interface, reduce lithium ion impedance of movement between electrode active material and solid electrolyte, so that All-solid lithium-ion battery has higher output, has good durability and cycle performance.
The third aspect, embodiments provides a kind of all-solid lithium-ion battery, including anode electrode, bears Pole electrode and sulfide base solid electrolyte, described anode electrode or negative electrode comprise the embodiment of the present invention On the one hand the all-solid lithium-ion battery compound electrode material provided.
Preferably, described sulfide base solid electrolyte is by Li2S and except Li2Sulfide composition beyond S, Described Li2S with except Li2The mol ratio of the sulfide beyond S is 50:50 ~ 95:5.
Preferably, the powder particle particle diameter of described sulfide base solid electrolyte is 0.5 μm ~ 5 μm, more preferably Ground, particle diameter is 0.5 μm ~ 1 μm.
Preferably, described except Li2Sulfide beyond S is SiS2、P2S5、B2S3、GeS2、Sb2S3、ZrSx、 FeSx、FeSxOr ZnSx, wherein, x=1 ~ 3.
The all-solid lithium-ion battery that the embodiment of the present invention third aspect provides has extended cycle life, and has excellent Discharge capacity and high rate performance.
The advantage of the embodiment of the present invention will partly illustrate, and a part according to description is It will be apparent that or can be known by the enforcement of the embodiment of the present invention.
Accompanying drawing explanation
Fig. 1 is the cycle performance test figure of the embodiment of the present invention 1 and the all-solid lithium-ion battery of comparative example 1.
Detailed description of the invention
The following stated is the preferred implementation of the embodiment of the present invention, it is noted that general for the art For logical technical staff, on the premise of without departing from embodiment of the present invention principle, it is also possible to make some improvement And retouching, these improvements and modifications are also considered as the protection domain of the embodiment of the present invention.
Embodiment of the present invention first aspect provides a kind of all-solid lithium-ion battery compound electrode material, to solve Certainly sulfide solid electrolyte easily reacts with electrode active material and decomposes, thus forms space charge layer, makes Interface between electrode/solid electrolyte forms the high impedance moving lithium ion, causes battery to have relatively low Output, relatively low durability and the problem of cycle performance.Embodiment of the present invention second aspect provides A kind of preparation method of all-solid lithium-ion battery compound electrode material.The embodiment of the present invention third aspect carries Supply a kind of all-solid lithium-ion battery.
First aspect, embodiments provides a kind of all-solid lithium-ion battery compound electrode material, bag Include electrode active material and be arranged on the clad on described electrode active material surface, described electrode active material For positive electrode active materials or negative active core-shell material, the material of described clad is counted by weight and is included: 0.1 ~ 20 The polymer of part polymer monomer and 0.1 ~ 50 part of ethylene glycol derivative formation, 0.1 ~ 10 part of lithium salts, 0.1 ~ 10 Part polymerization initiator and 50 ~ 99.9 parts of plasticizers, described polymer monomer is selected from fluorine-based polymer monomer, ethers One or more in polymer monomer, acrylic polymer monomer and acrylonitrile polymers monomer.
Compared with prior art, the all-solid lithium-ion battery compound electrode material that the present invention provides has cladding Layer, described clad is coated on described electrode active material surface as interface-modifying layer, and not with electrode Active material and solid electrolyte react.The present invention is coated on the clad on electrode active material surface, In all-solid lithium-ion battery, as electrode active material and the intermediate layer of solid electrolyte, can effectively press down Sulfide solid electrolyte S processed3P-S-SP3Crosslinking sulfur in division center and electrode active material react and Decompose, the formation of suppression space charge layer, suppress the formation of high interface impedance, from without reducing lithium ion Conductivity.All-solid lithium-ion battery compound electrode material finally can make battery have higher output work Rate, has good durability and stable circulation performance.
Described fluorine-based polymer monomer is vinylidene and/or biasfluoroethylene-hexafluoropropylene, ether polymer monomer For oxirane and/or expoxy propane, acrylic polymer monomer is methyl methacrylate.
Described ethylene glycol derivative is selected from ethylene glycol methacrylate, ethylene glycol dimethacrylate, second One or more in butanediol acrylate and glycol diacrylate.
Lithium salts is selected from lithium perchlorate LiClO4, LiBF4 LiBF4, lithium hexafluoro phosphate LiPF6, hexafluoro arsenic Acid lithium LiAsF6, trifluoromethyl sulfonic acid lithium LiCF3SO3With bis trifluoromethyl sulphonyl lithamide LiN (CF3SO2)2 In one or more.
Polymerization initiator is in azodiisobutyronitrile, benzoyl peroxide, acetyl peroxide and benzophenone One or more.
Plasticizer is selected from Allyl carbonate, dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate and ethylene carbonate One or more in ester.
The material of described clad also includes the additive of 0.1 ~ 30 part, and described additive is selected from Nano-meter SiO_22、 Nano-TiO2, nanometer Al2O3, single-layer carbon nano-tube, multilayer carbon nanotube, zeolite, montmorillonite and molecular sieve One or more in ZSM-5.The addition of described nanometer conductive material can improve clad mechanical performance and Ionic conductivity.
Positive electrode active materials is selected from cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, nickle cobalt lithium manganate, five oxygen Change one or more in two vanadium, molybdenum trioxide and titanium disulfide.
Negative active core-shell material is selected from graphite, hard carbon, silicon, silicon oxide compound, ashbury metal, lithium cobalt nitride, lithium One or more in metal and lithium alloy.
The thickness of clad can be 0.1 ~ 2000nm.The thickness of present embodiment clad is 0.1 ~ 1000nm.
Described clad does not contains electrode active material away from the side of electrode active material.
A kind of all-solid lithium-ion battery compound electrode material that embodiment of the present invention first aspect provides, can be very Effectively suppression sulfide solid electrolyte S3P-S-SP3Crosslinking sulfur in division center occurs with electrode active material React and decompose, the formation of suppression space charge layer, suppresses the formation of high interface impedance, from without reducing The conductivity of lithium ion；Additionally, described clad will not hinder lithium ion at electrode active material and solid-state electricity Solve the conduction between matter；Therefore, all-solid lithium-ion battery compound electrode material finally can make battery have Higher output, has good durability and cycle performance.
Second aspect, embodiments provides the system of a kind of all-solid lithium-ion battery compound electrode material Preparation Method, comprises the following steps:
Count by weight, take 0.1 ~ 20 part of polymer monomer, 0.1 ~ 50 part of ethylene glycol derivative, 0.1 ~ 10 Part lithium salts, 0.1 ~ 10 part of polymerization initiator and 50 ~ 99.9 parts of plasticizers, preparation obtains mixed solution, described poly- Monomer adduct is selected from fluorine-based polymer monomer, ether polymer monomer, acrylic polymer monomer and propylene One or more in nitrile polymer monomer；
Described mixed solution is arranged on by method of electrostatic spinning, electro-blown spinning method, liquid phase spraying process or print process Electrode active material surface, described electrode active material is positive electrode active materials or negative active core-shell material, subsequently Raw at described electrode active material surface aggregate by thermal polymerization, electron beam polymerization method or ultraviolet polymerization Become clad, prepare all-solid lithium-ion battery compound electrode material.
Described fluorine-based polymer monomer is vinylidene and/or biasfluoroethylene-hexafluoropropylene, ether polymer monomer For oxirane and/or expoxy propane, acrylic polymer monomer is methyl methacrylate.
Described ethylene glycol derivative is selected from ethylene glycol methacrylate, ethylene glycol dimethacrylate, second One or more in butanediol acrylate and glycol diacrylate.
Lithium salts is selected from lithium perchlorate LiClO4, LiBF4 LiBF4, lithium hexafluoro phosphate LiPF6, hexafluoro arsenic Acid lithium LiAsF6, trifluoromethyl sulfonic acid lithium LiCF3SO3With bis trifluoromethyl sulphonyl lithamide LiN (CF3SO2)2 In one or more.
Polymerization initiator is in azodiisobutyronitrile, benzoyl peroxide, acetyl peroxide and benzophenone One or more.
Plasticizer is selected from Allyl carbonate, dimethyl carbonate, diethyl carbonate, Ethyl methyl carbonate and ethylene carbonate One or more in ester.
Also including the additive adding 0.1 ~ 30 part during described preparation mixed solution, described additive selects From Nano-meter SiO_22, nano-TiO2, nanometer Al2O3, single-layer carbon nano-tube, multilayer carbon nanotube, zeolite, illiteracy One or more in de-stone and molecular sieve ZSM-5.
Positive electrode active materials is selected from cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, nickle cobalt lithium manganate, five oxygen Change one or more in two vanadium, molybdenum trioxide and titanium disulfide.
Negative active core-shell material is selected from graphite, hard carbon, silicon, silicon oxide compound, ashbury metal, lithium cobalt nitride, lithium One or more in metal and lithium alloy.
The thickness of clad can be 0.1 ~ 2000nm.In this enforcement, the thickness of clad is 0.1 ~ 1000nm.
Described clad does not contains electrode active material away from the side of electrode active material.
The system of a kind of all-solid lithium-ion battery compound electrode material that embodiment of the present invention second aspect provides Preparation Method is simple, and the all-solid lithium-ion battery compound electrode material prepared can improve electrode/solid-state electricity Solve matter interface, reduce lithium ion impedance of movement between electrode active material and solid electrolyte, so that All-solid lithium-ion battery has higher output, has good durability and cycle performance.
The third aspect, embodiments provides a kind of all-solid lithium-ion battery, including anode electrode, bears Pole electrode and sulfide base solid electrolyte, described anode electrode or negative electrode comprise the embodiment of the present invention On the one hand the all-solid lithium-ion battery compound electrode material provided.
Described sulfide base solid electrolyte is by Li2S and except Li2Sulfide composition beyond S, described Li2S With except Li2The mol ratio of the sulfide beyond S is 50:50 ~ 95:5.
The powder particle particle diameter of described sulfide base solid electrolyte is 0.5 μm ~ 5 μm, it is highly preferred that particle diameter It it is 0.5 μm ~ 1 μm.
Described except Li2Sulfide beyond S is SiS2、P2S5、B2S3、GeS2、Sb2S3、ZrSx、FeSx、 FeSxOr ZnSx, wherein, x=1 ~ 3.
The all-solid lithium-ion battery that the embodiment of the present invention third aspect provides has extended cycle life, and has excellent Discharge capacity and high rate performance.
Divide multiple embodiment that the embodiment of the present invention is further detailed below.Wherein, the present invention implements Example is not limited to following specific embodiment.In the range of constant principal right, can change by suitable carrying out Implement.
Embodiment 1
The preparation method of a kind of all-solid lithium-ion battery compound electrode material, comprises the following steps:
(1) count by weight, take 15 parts of vinylidenes, 20 parts of ethylene glycol methacrylates, 10 Part LiBF4 LiBF4, 5 parts of azodiisobutyronitriles and 50 parts of Allyl carbonaties, preparation obtains mixing molten Liquid；
(2) mixed solution is connected to rustless steel needle tubing by a conduit, and passes through with the flow of 0.4ml/h Needle tubing ejection mixed solution, with electrode active material as collecting body, and is 15cm with the vertical dimension of syringe needle, Ground connection simultaneously, is connected needle tubing and a high tension generator, and voltage is adjusted to 15v, will pass through by described mixed solution Method of electrostatic spinning is arranged on electrode active material surface, and described electrode active material is cobalt acid lithium；
Subsequently at 70 DEG C of thermal initiation in-situ polymerizations, i.e. poly-on described electrode active material surface by thermal polymerization The clad that symphysis becomes thickness to be 0.1nm, prepares all-solid lithium-ion battery compound electrode materials A 1.Institute State clad and do not contain electrode active material A1 away from the side of electrode active material.
The preparation method of all-solid lithium-ion battery
(1) Li is prepared2S-P2S5Base glass-ceramic electrolyte
It is the Li of 99.95% by purity2S and P2S5Planetary machinery is joined according to the ratio that mass ratio is 75:25 At room temperature ball milling 10h in ball mill, then by extruder grain, makes the granule that particle diameter is 0.5 ~ 5 μm, By spheroidal particle heat treatment 5h at 360 DEG C, then it is annealed to room temperature, obtains Li2S-P2S5Base glass-ceramic electricity Xie Zhi；
(2) by above-mentioned prepared compound electrode materials A 1 and Li2S-P2S5Base glass-ceramic electrolyte and negative pole Active electrode is assembled into all solid state secondary lithium battery core, and wherein, the material of negative pole is graphite, then uses aluminum plastic film It is packaged into battery and through chemical conversion, obtains all-solid lithium-ion battery.
Embodiment 2
The preparation method of a kind of all-solid lithium-ion battery compound electrode material, comprises the following steps:
(1) count by weight, take 15 parts of oxirane, 0.1 part of ethylene glycol dimethacrylate, 0.1 Part lithium hexafluoro phosphate LiPF6, 10 parts of benzoyl peroxides, 50 parts of dimethyl carbonate and 0.1 part of Nano-meter SiO_22, Preparation obtains mixed solution；
(2) mixed solution apparatus have the spinning head of air nozzle carry out spinning, spinning pressure is 5.88 × 105Pa, voltage is direct current 50kV, and the most described mixed solution is arranged on electrode active material by electro-blown spinning method Surface, described electrode active material is LiFePO4；
Solvent flashing in drying baker subsequently, causes polymerization (110W, λ=375nm) under uv light irradiation, Gu Changing temperature is 25 DEG C, is and generates thickness by ultraviolet polymerization at described electrode active material surface aggregate For the clad of 1000nm, prepare all-solid lithium-ion battery compound electrode materials A 2.Described clad Side away from electrode active material does not contains electrode active material A2.
The preparation method of all-solid lithium-ion battery as described in Example 1, differs only in use the present embodiment system The all-solid lithium-ion battery compound electrode materials A 2 obtained.
Embodiment 3
The preparation method of a kind of all-solid lithium-ion battery compound electrode material, comprises the following steps:
(1) count by weight, take 0.1 part of methyl methacrylate, 15 parts of EDIAs, 10 Part hexafluoroarsenate lithium LiAsF6, 0.1 part of acetyl peroxide and 50 parts of ethylene carbonates, preparation obtains mixing molten Liquid；
(2) being placed in by mixed solution in fluid plasma paint finishing, atomization gas is nitrogen, and pressure is 0.7MPa, voltage is 40V, and electric current is 600A, will be arranged on by liquid phase spraying process by described mixed solution Electrode active material surface, described electrode active material is graphite；
Solvent flashing in drying baker subsequently, utilizes electron beam polymerization method to cause and is polymerized, accelerating potential 200KV, Process velocity is at 5m/min, and irradiating width is 20cm, i.e. by electron beam polymerization method at described electrode activity material It is the clad of 2000nm that material surface aggregate generates thickness, prepares all-solid lithium-ion battery compound electrode material Material A3.Described clad does not contains electrode active material A3 away from the side of electrode active material.
The preparation method of all-solid lithium-ion battery as described in Example 1, differs only in use the present embodiment The all-solid lithium-ion battery compound electrode materials A 3 prepared.
Embodiment 4
The preparation method of a kind of all-solid lithium-ion battery compound electrode material, comprises the following steps:
(1) count by weight, take 10 parts of vinylidenes and 10 parts of expoxy propane, 50 parts of ethylene glycol dipropyls Olefin(e) acid ester, 5 parts of trifluoromethyl sulfonic acid lithium LiCF3SO3, 5 parts of benzophenone, 50 parts of diethyl carbonates and 30 Part single-layer carbon nano-tube, preparation obtains mixed solution；
(2) described mixed solution is arranged on electrode active material surface, described electrode activity by print process Material is silicon oxide compound, is generated at described electrode active material surface aggregate by 80 DEG C of thermal polymerization subsequently Thickness is the clad of 100nm, prepares all-solid lithium-ion battery compound electrode materials A 4.Described cladding Layer does not contains electrode active material A4 away from the side of electrode active material.
The preparation method of all-solid lithium-ion battery as described in Example 1, differs only in use the present embodiment The all-solid lithium-ion battery compound electrode materials A 4 prepared.
Embodiment 5
The preparation method of a kind of all-solid lithium-ion battery compound electrode material, comprises the following steps:
(1) count by weight, take 10 parts of biasfluoroethylene-hexafluoropropylenes and 5 parts of methyl methacrylates, 5 Part ethylene glycol methacrylate and 5 parts of ethylene glycol dimethacrylates, 5 parts of bis trifluoromethyl sulphonyl ammonia Change lithium LiN (CF3SO2)2, 2.5 parts of azodiisobutyronitriles and 2.5 parts of benzophenone, and 99.9 parts of carbonic acid first Ethyl ester, also 10 parts of zeolites, preparation obtains mixed solution；
(2) mixed solution is connected to rustless steel needle tubing by a conduit, and passes through with the flow of 0.4ml/h Needle tubing ejection mixed solution, with electrode active material as collecting body, and is 15cm with the vertical dimension of syringe needle, Ground connection simultaneously, is connected needle tubing and a high tension generator, and voltage is adjusted to 15v, will pass through by described mixed solution Method of electrostatic spinning is arranged on electrode active material surface, and described electrode active material is molybdenum trioxide；
Solvent flashing in drying baker subsequently, causes polymerization (110W, λ=375nm) under uv light irradiation, Solidification temperature is 85 DEG C, is and generates thickness by ultraviolet polymerization at described electrode active material surface aggregate Degree is the clad of 50nm, prepares all-solid lithium-ion battery compound electrode materials A 5.Described clad is remote The side of ionization electrode active material does not contains electrode active material A5.
The preparation method of all-solid lithium-ion battery as described in Example 1, differs only in use the present embodiment The all-solid lithium-ion battery compound electrode materials A 5 prepared.
Comparative example 1
By commercially available uncoated electrode active material cobalt acid lithium (LiCoO2) it is assembled into all-solid lithium-ion battery, Wherein, the material of negative pole is graphite, and solid electrolyte is embodiment 1 gained Li2S-P2S5Base glass-ceramic electricity Xie Zhi.
Effect example
Beneficial effect for bringing embodiment of the present invention technical scheme provides powerful support for, and special offer is following to follow Ring volumetric properties is tested:
All-solid lithium-ion battery embodiment 1 being assembled into comparative example 1, at the voltage model of 3.0 ~ 4.4V In enclosing, carrying out charge-discharge test under 0.5C, its test result is as shown in Figure 1.It can be seen that warp The cobalt acid lithium (LiCoO of clad cladding2), after 600 times circulate, capability retention is 87.7%, and Uncoated cobalt acid lithium (LiCoO2), after 600 times circulate, capability retention is only 80.0%, by This is visible, the cobalt acid lithium (LiCoO after cladding2) cycle performance is significantly improved.

Claims (10)

1. an all-solid lithium-ion battery compound electrode material, it is characterised in that include electrode activity material Expecting and be arranged on the clad on described electrode active material surface, described electrode active material is positive-active material Expecting or negative active core-shell material, the material of described clad is counted by weight and is included: 0.1～20 part of polymer list Body and the polymer of 0.1～50 part of ethylene glycol derivative formation, 0.1～10 part of lithium salts, 0.1～10 part of polymerization cause Agent and 50～99.9 parts of plasticizers, described polymer monomer is selected from fluorine-based polymer monomer, ether polymer monomer With the one in acrylonitrile polymers monomer, or selected from fluorine-based polymer monomer, ether polymer monomer, Several in acrylic polymer monomer and acrylonitrile polymers monomer.
2. a kind of all-solid lithium-ion battery compound electrode material as claimed in claim 1, its feature exists In, described fluorine-based polymer monomer is vinylidene and/or biasfluoroethylene-hexafluoropropylene, ether polymer monomer For oxirane and/or expoxy propane, acrylic polymer monomer is methyl methacrylate.
3. a kind of all-solid lithium-ion battery compound electrode material as claimed in claim 1, its feature exists In, described ethylene glycol derivative selected from ethylene glycol methacrylate, ethylene glycol dimethacrylate, One or more in EDIA and glycol diacrylate.
4. a kind of all-solid lithium-ion battery compound electrode material as claimed in claim 1, its feature exists In, the material of described clad also includes the additive of 0.1～30 part, and described additive is selected from Nano-meter SiO_22、 Nano-TiO2, nanometer Al2O3, single-layer carbon nano-tube, multilayer carbon nanotube, zeolite, montmorillonite and molecular sieve One or more in ZSM-5.
5. a kind of all-solid lithium-ion battery compound electrode material as claimed in claim 1, its feature exists In, the thickness of clad is 0.1～2000nm.
6. a kind of all-solid lithium-ion battery compound electrode material as claimed in claim 1, its feature exists In, described clad does not contains electrode active material away from the side of electrode active material.
7. the preparation method of an all-solid lithium-ion battery compound electrode material, it is characterised in that include Following steps:
Count by weight, take 0.1～20 part of polymer monomer, 0.1～50 part of ethylene glycol derivative, 0.1～10 Part lithium salts, 0.1～10 part of polymerization initiator and 50～99.9 parts of plasticizers, preparation obtains mixed solution, described poly- Monomer adduct is selected from fluorine-based polymer monomer, ether polymer monomer and acrylonitrile polymers monomer Kind, or selected from fluorine-based polymer monomer, ether polymer monomer, acrylic polymer monomer and acrylonitrile Several in base polymer monomer；
Described mixed solution is arranged on by method of electrostatic spinning, electro-blown spinning method, liquid phase spraying process or print process Electrode active material surface, described electrode active material is positive electrode active materials or negative active core-shell material, subsequently Raw at described electrode active material surface aggregate by thermal polymerization, electron beam polymerization method or ultraviolet polymerization Become clad, prepare all-solid lithium-ion battery compound electrode material.
The preparation method of a kind of all-solid lithium-ion battery compound electrode material the most as claimed in claim 7, It is characterized in that, described fluorine-based polymer monomer is vinylidene and/or biasfluoroethylene-hexafluoropropylene, and ethers gathers Monomer adduct is oxirane and/or expoxy propane, and acrylic polymer monomer is methyl methacrylate.
The preparation method of a kind of all-solid lithium-ion battery compound electrode material the most as claimed in claim 7, It is characterized in that, described ethylene glycol derivative is selected from ethylene glycol methacrylate, ethylene glycol dimethyl third One or more in olefin(e) acid ester, EDIA and glycol diacrylate.
10. an all-solid lithium-ion battery, including anode electrode, negative electrode and sulfide base solid state electrolysis Matter, the all-solid lithium-ion battery that described anode electrode or negative electrode comprise described in claim 1 is compound Electrode material.
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