CN103682354A - All-solid-state lithium ion battery composite electrode material and preparation method thereof and all-solid-state lithium ion battery - Google Patents
All-solid-state lithium ion battery composite electrode material and preparation method thereof and all-solid-state lithium ion battery Download PDFInfo
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- CN103682354A CN103682354A CN201210345669.5A CN201210345669A CN103682354A CN 103682354 A CN103682354 A CN 103682354A CN 201210345669 A CN201210345669 A CN 201210345669A CN 103682354 A CN103682354 A CN 103682354A
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Abstract
The embodiment of the invention provides an all-solid-state lithium ion battery composite electrode material, which comprises an electrode active material and a coating layer arranged on the surface of the electrode active material, wherein the coating layer comprises the compositions in parts by weight: 0.1-20 parts of polymer monomers, 0.1-50 parts of polymers formed by glycol derivatives, 0.1-10 parts of lithium salt, 0.1-10 parts of polymerization initiator, and 50-99.9 parts of plasticizer, and the polymer monomers are selected from one or more of fluorine polymer monomers, ether polymer monomers, acrylic acid polymer monomers and acrylonitrile polymer monomers. The coating layer can effectively inhibit the formation of a space charge layer, and is beneficial to reduction on the interface resistance of an all-solid-state lithium ion battery, thus improving the cycle stability and durability of the all-solid-state battery. The embodiment of the invention also provides a preparation method of the all-solid-state lithium ion battery composite electrode material, and an all-solid-state lithium ion battery comprising the composite electrode material.
Description
Technical field
The present invention relates to lithium ion battery field, particularly relate to a kind of all solid state lithium ion battery compound electrode material and preparation method thereof and all solid state lithium ion battery.
Background technology
From last century the nineties, in numerous energy substitution products, lithium ion battery is subject to people's close attention with features such as higher energy density, good cycle performance, memory-less effects.
In recent years, increase along with electric motor car and large-scale fixation equipment electric power storage purposes battery applications demand, having safe and long-life all solid state lithium ion battery starts to be attracted attention, it adopts the solid-state inorganic matter not firing as electrolyte, not only there is higher energy density, and there is the advantages such as good security and stability, erecting device are simple, low cost of manufacture simultaneously.
Main research at present concentrates on the inorganic solid electrolyte of application the material that Oxide and sulfide is relevant mostly, compares with oxide, and sulfide is favored by researchers owing to having the stronger good characteristics such as ionic conductivity.Yet, in application, there is a common problem in sulfide solid electrolyte, in electrode/solid electrolyte interface, the sulfide solid electrolyte with the chalcogen of crosslinked sulphur representative easily reacts with electrode active material and decomposes, thereby formation space charge layer, make the interface between electrode/solid electrolyte form the high impedance that lithium ion is moved, cause battery to there is lower power output, lower durability and cycle performance.
Summary of the invention
Given this, embodiment of the present invention first aspect provides a kind of all solid state lithium ion battery compound electrode material, to solve sulfide solid electrolyte, easily react with electrode active material and decompose, thereby formation space charge layer, make the interface between electrode/solid electrolyte form the high impedance that lithium ion is moved, cause battery to there is lower power output, lower durability and the problem of cycle performance.Embodiment of the present invention second aspect provides a kind of preparation method of all solid state lithium ion battery compound electrode material.The embodiment of the present invention third aspect provides a kind of all solid state lithium ion battery.
First aspect, the embodiment of the present invention provides a kind of all solid state lithium ion battery compound electrode material, comprise electrode active material and the coating layer that is arranged on described electrode active material surface, described electrode active material is positive electrode active materials or negative active core-shell material, the material of described coating layer is counted and is comprised by weight: 0.1 ~ 20 part of polymer monomer and 0.1 ~ 50 part of polymer that ethylene glycol derivative forms, 0.1 ~ 10 part of lithium salts, 0.1 ~ 10 part of polymerization initiator and 50 ~ 99.9 parts of plasticizer, described polymer monomer is selected from fluorine-based polymer monomer, ether polymer monomer, one or more in acrylic polymer monomer and vinyl cyanide polymer monomer.
Compared with prior art, all solid state lithium ion battery compound electrode material provided by the invention has coating layer, described coating layer is coated on described electrode active material surface as modifying interface layer, and does not react with electrode active material and solid electrolyte.In the present invention, be coated on the coating layer on electrode active material surface, in all solid state lithium ion battery, as the intermediate layer of electrode active material and solid electrolyte, can effectively suppress sulfide solid electrolyte S
3p-S-SP
3crosslinked sulphur and electrode active material in division center react and decompose, and suppress the formation of space charge layer, suppress the formation of high interface impedance, thereby can not reduce the conductibility of lithium ion.All solid state lithium ion battery compound electrode material finally can make battery have higher power output, has good durability and stable circulation performance.
Preferably, described fluorine-based polymer monomer is vinylidene and/or biasfluoroethylene-hexafluoropropylene, and ether polymer monomer is oxirane and/or expoxy propane, and acrylic polymer monomer is methyl methacrylate.
Preferably, described ethylene glycol derivative is selected from one or more in ethylene glycol methacrylate, ethylene glycol dimethacrylate, EDIA and glycol diacrylate.
Preferably, lithium salts is selected from lithium perchlorate LiClO
4, LiBF4 LiBF
4, lithium hexafluoro phosphate LiPF
6, hexafluoroarsenate lithium LiAsF
6, trifluoromethyl sulfonic acid lithium LiCF
3sO
3with bis trifluoromethyl sulphonyl lithamide LiN (CF
3sO
2)
2in one or more.
Preferably, polymerization initiator is selected from one or more in azodiisobutyronitrile, benzoyl peroxide, acetyl peroxide and benzophenone.
Preferably, plasticizer is selected from one or more in propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and ethylene carbonate.
Preferably, the material of described coating layer also comprises the additive of 0.1 ~ 30 part, and described additive is selected from nanometer SiO
2, nano-TiO
2, nanometer Al
2o
3, one or more in single-layer carbon nano-tube, multilayer carbon nanotube, zeolite, montmorillonite and molecular sieve ZSM-5.
Preferably, positive electrode active materials is selected from cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, nickle cobalt lithium manganate, vanadic oxide, one or more in molybdenum trioxide and titanium disulfide.
Preferably, negative active core-shell material is selected from one or more in graphite, hard carbon, silicon, silicon oxide compound, ashbury metal, lithium cobalt nitride, lithium metal and lithium alloy.
Preferably, the thickness of coating layer is 0.1 ~ 2000nm.More preferably, the thickness of coating layer is 0.1 ~ 1000nm.
Preferably, described coating layer does not contain electrode active material away from a side of electrode active material.
A kind of all solid state lithium ion battery compound electrode material that embodiment of the present invention first aspect provides, can very effectively suppress sulfide solid electrolyte S
3p-S-SP
3crosslinked sulphur and electrode active material in division center react and decompose, and suppress the formation of space charge layer, suppress the formation of high interface impedance, thereby can not reduce the conductibility of lithium ion; In addition, described coating layer can not hinder the conduction of lithium ion between electrode active material and solid electrolyte; Therefore, all solid state lithium ion battery compound electrode material finally can make battery have higher power output, has good durability and cycle performance.
Second aspect, the embodiment of the present invention provides a kind of preparation method of all solid state lithium ion battery compound electrode material, 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 of lithium salts, 0.1 ~ 10 part of polymerization initiator and 50 ~ 99.9 parts of plasticizer, preparation obtains mixed solution, and described polymer monomer is selected from one or more in fluorine-based polymer monomer, ether polymer monomer, acrylic polymer monomer and vinyl cyanide polymer monomer;
Described mixed solution is blown to spin processes, liquid phase spraying process or print process by method of electrostatic spinning, electricity and be arranged on electrode active material surface, described electrode active material is positive electrode active materials or negative active core-shell material, by legal, the electron beam polymerization method of hot polymerization or polymerizable ultraviolet method, at described electrode active material surface aggregate, generate coating layer subsequently, make all solid state lithium ion battery compound electrode material.
Preferably, described fluorine-based polymer monomer is vinylidene and/or biasfluoroethylene-hexafluoropropylene, and ether polymer monomer is oxirane and/or expoxy propane, and acrylic polymer monomer is methyl methacrylate.
Preferably, described ethylene glycol derivative is selected from one or more in ethylene glycol methacrylate, ethylene glycol dimethacrylate, EDIA and glycol diacrylate.
Preferably, lithium salts is selected from lithium perchlorate LiClO
4, LiBF4 LiBF
4, lithium hexafluoro phosphate LiPF
6, hexafluoroarsenate lithium LiAsF
6, trifluoromethyl sulfonic acid lithium LiCF
3sO
3with bis trifluoromethyl sulphonyl lithamide LiN (CF
3sO
2)
2in one or more.
Preferably, polymerization initiator is selected from one or more in azodiisobutyronitrile, benzoyl peroxide, acetyl peroxide and benzophenone.
Preferably, plasticizer is selected from one or more in propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and ethylene carbonate.
Preferably, also comprise the additive that adds 0.1 ~ 30 part in the process of described preparation mixed solution, described additive is selected from nanometer SiO
2, nano-TiO
2, nanometer Al
2o
3, one or more in single-layer carbon nano-tube, multilayer carbon nanotube, zeolite, montmorillonite and molecular sieve ZSM-5.
Preferably, positive electrode active materials is selected from cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, nickle cobalt lithium manganate, vanadic oxide, one or more in molybdenum trioxide and titanium disulfide.
Preferably, negative active core-shell material is selected from one or more in graphite, hard carbon, silicon, silicon oxide compound, ashbury metal, lithium cobalt nitride, lithium metal and lithium alloy.
Preferably, the thickness of coating layer is 0.1 ~ 2000nm.More preferably, the thickness of coating layer is 0.1 ~ 1000nm.
Preferably, described coating layer does not contain electrode active material away from a side of electrode active material.
The preparation method of a kind of all solid state lithium ion battery compound electrode material that embodiment of the present invention second aspect provides is simple, the all solid state lithium ion battery compound electrode material making can improve electrode/solid electrolyte interface, reduce the impedance that lithium ion moves between electrode active material and solid electrolyte, thereby make all solid state lithium ion battery there is higher power output, there is good durability and cycle performance.
The third aspect, the embodiment of the present invention provides a kind of all solid state lithium ion battery, comprise anode electrode, negative electrode and sulfide base solid electrolyte, described anode electrode or negative electrode comprise all solid state lithium ion battery compound electrode material that embodiment of the present invention first aspect provides.
Preferably, described sulfide base solid electrolyte is by Li
2s and except Li
2sulfide beyond S forms, described Li
2s with except Li
2the 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 μ m ~ 5 μ m, and more preferably, particle diameter is 0.5 μ m ~ 1 μ m.
Preferably, described except Li
2sulfide beyond S is SiS
2, P
2s
5, B
2s
3, GeS
2, Sb
2s
3, ZrS
x, FeS
x, FeS
xor ZnS
x, wherein, x=1 ~ 3.
The all solid state lithium ion battery cycle life that the embodiment of the present invention third aspect provides is long, and has good discharge capacity and high rate performance.
The advantage of the embodiment of the present invention will partly be illustrated in the following description, and a part is apparent according to specification, or can know by the enforcement of the embodiment of the present invention.
Accompanying drawing explanation
Fig. 1 is the cycle performance resolution chart of all solid state lithium ion battery of the embodiment of the present invention 1 and comparative example 1.
Embodiment
The following stated is the preferred implementation of the embodiment of the present invention; should be understood that; for those skilled in the art; do not departing under the prerequisite of embodiment of the present invention principle; can also make some improvements and modifications, these improvements and modifications are also considered as the protection range of the embodiment of the present invention.
Embodiment of the present invention first aspect provides a kind of all solid state lithium ion battery compound electrode material, to solve sulfide solid electrolyte, easily react with electrode active material and decompose, thereby formation space charge layer, make the interface between electrode/solid electrolyte form the high impedance that lithium ion is moved, cause battery to there is lower power output, lower durability and the problem of cycle performance.Embodiment of the present invention second aspect provides a kind of preparation method of all solid state lithium ion battery compound electrode material.The embodiment of the present invention third aspect provides a kind of all solid state lithium ion battery.
First aspect, the embodiment of the present invention provides a kind of all solid state lithium ion battery compound electrode material, comprise electrode active material and the coating layer that is arranged on described electrode active material surface, described electrode active material is positive electrode active materials or negative active core-shell material, the material of described coating layer is counted and is comprised by weight: 0.1 ~ 20 part of polymer monomer and 0.1 ~ 50 part of polymer that ethylene glycol derivative forms, 0.1 ~ 10 part of lithium salts, 0.1 ~ 10 part of polymerization initiator and 50 ~ 99.9 parts of plasticizer, described polymer monomer is selected from fluorine-based polymer monomer, ether polymer monomer, one or more in acrylic polymer monomer and vinyl cyanide polymer monomer.
Compared with prior art, all solid state lithium ion battery compound electrode material provided by the invention has coating layer, described coating layer is coated on described electrode active material surface as modifying interface layer, and does not react with electrode active material and solid electrolyte.In the present invention, be coated on the coating layer on electrode active material surface, in all solid state lithium ion battery, as the intermediate layer of electrode active material and solid electrolyte, can effectively suppress sulfide solid electrolyte S
3p-S-SP
3crosslinked sulphur and electrode active material in division center react and decompose, and suppress the formation of space charge layer, suppress the formation of high interface impedance, thereby can not reduce the conductibility of lithium ion.All solid state lithium ion battery compound electrode material finally can make battery have higher power output, has good durability and stable circulation performance.
Described fluorine-based polymer monomer is vinylidene and/or biasfluoroethylene-hexafluoropropylene, and ether polymer monomer is oxirane and/or expoxy propane, and acrylic polymer monomer is methyl methacrylate.
Described ethylene glycol derivative is selected from one or more in ethylene glycol methacrylate, ethylene glycol dimethacrylate, EDIA and glycol diacrylate.
Lithium salts is selected from lithium perchlorate LiClO
4, LiBF4 LiBF
4, lithium hexafluoro phosphate LiPF
6, hexafluoroarsenate lithium LiAsF
6, trifluoromethyl sulfonic acid lithium LiCF
3sO
3with bis trifluoromethyl sulphonyl lithamide LiN (CF
3sO
2)
2in one or more.
Polymerization initiator is selected from one or more in azodiisobutyronitrile, benzoyl peroxide, acetyl peroxide and benzophenone.
Plasticizer is selected from one or more in propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and ethylene carbonate.
The material of described coating layer also comprises the additive of 0.1 ~ 30 part, and described additive is selected from nanometer SiO
2, nano-TiO
2, nanometer Al
2o
3, one or more in single-layer carbon nano-tube, multilayer carbon nanotube, zeolite, montmorillonite and molecular sieve ZSM-5.Described nanometer conductive material add mechanical performance and the ionic conductivity that can improve coating layer.
Positive electrode active materials is selected from cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, nickle cobalt lithium manganate, vanadic oxide, one or more in molybdenum trioxide and titanium disulfide.
Negative active core-shell material is selected from one or more in graphite, hard carbon, silicon, silicon oxide compound, ashbury metal, lithium cobalt nitride, lithium metal and lithium alloy.
The thickness of coating layer can be 0.1 ~ 2000nm.The thickness of present embodiment coating layer is 0.1 ~ 1000nm.
Described coating layer does not contain electrode active material away from a side of electrode active material.
A kind of all solid state lithium ion battery compound electrode material that embodiment of the present invention first aspect provides, can very effectively suppress sulfide solid electrolyte S
3p-S-SP
3crosslinked sulphur and electrode active material in division center react and decompose, and suppress the formation of space charge layer, suppress the formation of high interface impedance, thereby can not reduce the conductibility of lithium ion; In addition, described coating layer can not hinder the conduction of lithium ion between electrode active material and solid electrolyte; Therefore, all solid state lithium ion battery compound electrode material finally can make battery have higher power output, has good durability and cycle performance.
Second aspect, the embodiment of the present invention provides a kind of preparation method of all solid state lithium ion battery compound electrode material, comprises the following steps:
Count by weight, get 0.1 ~ 20 part of polymer monomer, 0.1 ~ 50 part of ethylene glycol derivative, 0.1 ~ 10 part of lithium salts, 0.1 ~ 10 part of polymerization initiator and 50 ~ 99.9 parts of plasticizer, preparation obtains mixed solution, and described polymer monomer is selected from one or more in fluorine-based polymer monomer, ether polymer monomer, acrylic polymer monomer and vinyl cyanide polymer monomer;
Described mixed solution is blown to spin processes, liquid phase spraying process or print process by method of electrostatic spinning, electricity and be arranged on electrode active material surface, described electrode active material is positive electrode active materials or negative active core-shell material, by legal, the electron beam polymerization method of hot polymerization or polymerizable ultraviolet method, at described electrode active material surface aggregate, generate coating layer subsequently, make all solid state lithium ion battery compound electrode material.
Described fluorine-based polymer monomer is vinylidene and/or biasfluoroethylene-hexafluoropropylene, and ether polymer monomer is oxirane and/or expoxy propane, and acrylic polymer monomer is methyl methacrylate.
Described ethylene glycol derivative is selected from one or more in ethylene glycol methacrylate, ethylene glycol dimethacrylate, EDIA and glycol diacrylate.
Lithium salts is selected from lithium perchlorate LiClO
4, LiBF4 LiBF
4, lithium hexafluoro phosphate LiPF
6, hexafluoroarsenate lithium LiAsF
6, trifluoromethyl sulfonic acid lithium LiCF
3sO
3with bis trifluoromethyl sulphonyl lithamide LiN (CF
3sO
2)
2in one or more.
Polymerization initiator is selected from one or more in azodiisobutyronitrile, benzoyl peroxide, acetyl peroxide and benzophenone.
Plasticizer is selected from one or more in propene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and ethylene carbonate.
In the process of described preparation mixed solution, also comprise the additive that adds 0.1 ~ 30 part, described additive is selected from nanometer SiO
2, nano-TiO
2, nanometer Al
2o
3, one or more in single-layer carbon nano-tube, multilayer carbon nanotube, zeolite, montmorillonite and molecular sieve ZSM-5.
Positive electrode active materials is selected from cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, nickle cobalt lithium manganate, vanadic oxide, one or more in molybdenum trioxide and titanium disulfide.
Negative active core-shell material is selected from one or more in graphite, hard carbon, silicon, silicon oxide compound, ashbury metal, lithium cobalt nitride, lithium metal and lithium alloy.
The thickness of coating layer can be 0.1 ~ 2000nm.In this enforcement, the thickness of coating layer is 0.1 ~ 1000nm.
Described coating layer does not contain electrode active material away from a side of electrode active material.
The preparation method of a kind of all solid state lithium ion battery compound electrode material that embodiment of the present invention second aspect provides is simple, the all solid state lithium ion battery compound electrode material making can improve electrode/solid electrolyte interface, reduce the impedance that lithium ion moves between electrode active material and solid electrolyte, thereby make all solid state lithium ion battery there is higher power output, there is good durability and cycle performance.
The third aspect, the embodiment of the present invention provides a kind of all solid state lithium ion battery, comprise anode electrode, negative electrode and sulfide base solid electrolyte, described anode electrode or negative electrode comprise all solid state lithium ion battery compound electrode material that embodiment of the present invention first aspect provides.
Described sulfide base solid electrolyte is by Li
2s and except Li
2sulfide beyond S forms, described Li
2s with except Li
2the 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 μ m ~ 5 μ m, and more preferably, particle diameter is 0.5 μ m ~ 1 μ m.
Described except Li
2sulfide beyond S is SiS
2, P
2s
5, B
2s
3, GeS
2, Sb
2s
3, ZrS
x, FeS
x, FeS
xor ZnS
x, wherein, x=1 ~ 3.
The all solid state lithium ion battery cycle life that the embodiment of the present invention third aspect provides is long, and has good discharge capacity and high rate performance.
Divide a plurality of embodiment to be further detailed the embodiment of the present invention below.Wherein, the embodiment of the present invention is not limited to following specific embodiment.In the scope of constant principal right, carrying out change that can be suitable is implemented.
A preparation method for all solid state lithium ion battery compound electrode material, comprises the following steps:
(1) count by weight, get 15 parts of vinylidenes, 20 parts of ethylene glycol methacrylates, 10 parts of LiBF4 LiBF
4, 5 parts of azodiisobutyronitriles and 50 parts of propene carbonates, preparation obtains mixed solution;
(2) mixed solution is connected to stainless steel needle tubing by a conduit, and by needle tubing, spray mixed solution with the flow of 0.4ml/h, with electrode active material as collection body, and with the vertical range of syringe needle be 15cm, ground connection, is connected needle tubing with a high pressure generator simultaneously, and voltage is adjusted to 15v, be about to described mixed solution and be arranged on electrode active material surface by method of electrostatic spinning, described electrode active material is cobalt acid lithium;
70 ℃ of heat, cause in-situ polymerization subsequently, by hot polymerization is legal, at described electrode active material surface aggregate, generate the coating layer that thickness is 0.1nm, make all solid state lithium ion battery compound electrode materials A 1.Described coating layer does not contain electrode active material A1 away from a side of electrode active material.
The preparation method of all solid state lithium ion battery
(1) prepare Li
2s-P
2s
5base glass-ceramic electrolyte
The Li that is 99.95% by purity
2s and P
2s
5the ratio that is 75:25 according to mass ratio joins in planetary mechanical ball grinding machine at room temperature ball milling 10h, then, by extruder grain, makes the particle that particle diameter is 0.5 ~ 5 μ m, by spheric granules heat treatment 5h at 360 ℃, is then annealed to room temperature, obtains Li
2s-P
2s
5base glass-ceramic electrolyte;
(2) by above-mentioned compound electrode materials A 1 and the Li making
2s-P
2s
5base glass-ceramic electrolyte becomes all solid state secondary lithium cell with negative electrode active electrode assembling, wherein, the material of negative pole is graphite, then with aluminum plastic film, is packaged into battery and through changing into, obtains all solid state lithium ion battery.
Embodiment 2
A preparation method for all solid state lithium ion battery compound electrode material, comprises the following steps:
(1) count by weight, get 15 parts of oxirane, 0.1 part of ethylene glycol dimethacrylate, 0.1 part of lithium hexafluoro phosphate LiPF
6, 10 parts of benzoyl peroxides, 50 parts of dimethyl carbonates and 0.1 part of nanometer SiO
2, preparation obtains mixed solution;
(2) mixed solution apparatus is had the spinning head of air nozzle carry out spinning, spinning pressure is 5.88 * 10
5pa, voltage is direct current 50kV, and described mixed solution blows spin processes by electricity and is arranged on electrode active material surface, and described electrode active material is LiFePO4;
Solvent flashing in drying box subsequently, initiated polymerization (110W under uv light irradiation, λ=375nm), curing temperature is 25 ℃, be by polymerizable ultraviolet method and generate at described electrode active material surface aggregate the coating layer that thickness is 1000nm, make all solid state lithium ion battery compound electrode materials A 2.Described coating layer does not contain electrode active material A2 away from a side of electrode active material.
As described in Example 1, difference is only all solid state lithium ion battery compound electrode materials A 2 of using the present embodiment to make to the preparation method of all solid state lithium ion battery.
Embodiment 3
A preparation method for all solid state lithium ion battery compound electrode material, comprises the following steps:
(1) count by weight, get 0.1 part of methyl methacrylate, 15 parts of EDIAs, 10 parts of hexafluoroarsenate lithium LiAsF
6, 0.1 part of acetyl peroxide and 50 parts of ethylene carbonates, preparation obtains mixed solution;
(2) mixed solution is placed in to liquid plasma spray system, atomization gas is nitrogen, and pressure is 0.7MPa, voltage is 40V, electric current is 600A, is about to described mixed solution and is arranged on electrode active material surface by liquid phase spraying process, and described electrode active material is graphite;
Solvent flashing in drying box subsequently, utilize electron beam polymerization method initiated polymerization, accelerating voltage 200KV, process velocity is at 5m/min, irradiating width is 20cm, by electron beam polymerization method, at described electrode active material surface aggregate, generate the coating layer that thickness is 2000nm, make all solid state lithium ion battery compound electrode materials A 3.Described coating layer does not contain electrode active material A3 away from a side of electrode active material.
As described in Example 1, difference is only all solid state lithium ion battery compound electrode materials A 3 of using the present embodiment to make to the preparation method of all solid state lithium ion battery.
Embodiment 4
A preparation method for all solid state lithium ion battery compound electrode material, comprises the following steps:
(1) count by weight, get 10 parts of vinylidenes and 10 parts of expoxy propane, 50 parts of glycol diacrylates, 5 parts of trifluoromethyl sulfonic acid lithium LiCF
3sO
3, 5 parts of benzophenone, 50 parts of diethyl carbonates and 30 parts of single-layer carbon nano-tubes, preparation obtains mixed solution;
(2) described mixed solution is arranged on to electrode active material surface by print process, described electrode active material is silicon oxide compound, by 80 ℃ of legal coating layers that are 100nm at described electrode active material surface aggregate generation thickness of hot polymerization, make all solid state lithium ion battery compound electrode materials A 4 subsequently.Described coating layer does not contain electrode active material A4 away from a side of electrode active material.
As described in Example 1, difference is only all solid state lithium ion battery compound electrode materials A 4 of using the present embodiment to make to the preparation method of all solid state lithium ion battery.
Embodiment 5
A preparation method for all solid state lithium ion battery compound electrode material, comprises the following steps:
(1) count by weight, get 10 parts of biasfluoroethylene-hexafluoropropylenes and 5 parts of methyl methacrylates, 5 parts of ethylene glycol methacrylates and 5 parts of ethylene glycol dimethacrylates, 5 parts of bis trifluoromethyl sulphonyl lithamide LiN (CF
3sO
2)
2, 2.5 parts of azodiisobutyronitriles and 2.5 parts of benzophenone, and 99.9 parts of methyl ethyl carbonates, also have 10 parts of zeolites, and preparation obtains mixed solution;
(2) mixed solution is connected to stainless steel needle tubing by a conduit, and by needle tubing, spray mixed solution with the flow of 0.4ml/h, with electrode active material as collection body, and with the vertical range of syringe needle be 15cm, ground connection, is connected needle tubing with a high pressure generator simultaneously, and voltage is adjusted to 15v, be about to described mixed solution and be arranged on electrode active material surface by method of electrostatic spinning, described electrode active material is molybdenum trioxide;
Solvent flashing in drying box subsequently, initiated polymerization (110W under uv light irradiation, λ=375nm), curing temperature is 85 ℃, be by polymerizable ultraviolet method and generate at described electrode active material surface aggregate the coating layer that thickness is 50nm, make all solid state lithium ion battery compound electrode materials A 5.Described coating layer does not contain electrode active material A5 away from a side of electrode active material.
As described in Example 1, difference is only all solid state lithium ion battery compound electrode materials A 5 of using the present embodiment to make to the preparation method of all solid state lithium ion battery.
Comparative example 1
By commercially available not coated electrode active material cobalt acid lithium (LiCoO
2) be assembled into all solid state lithium ion battery, wherein, the material of negative pole is graphite, solid electrolyte is embodiment 1 gained Li
2s-P
2s
5base glass-ceramic electrolyte.
Effect embodiment
For the beneficial effect that embodiment of the present invention technical scheme is brought provides powerful support for, spy provides following circulation volume performance test:
By embodiment 1 and all solid state lithium ion battery that comparative example 1 is assembled into, in the voltage range of 3.0 ~ 4.4V, under 0.5C, carry out charge-discharge test, its test result is as shown in Figure 1.As can be seen from the figure, through the coated cobalt acid lithium (LiCoO of coating layer
2), after 600 circulations, capability retention is 87.7%, and uncoated cobalt acid lithium (LiCoO
2), after 600 circulations, capability retention is only 80.0%, as can be seen here, and the cobalt acid lithium (LiCoO after being coated
2) cycle performance is significantly improved.
Claims (10)
1. an all solid state lithium ion battery compound electrode material, it is characterized in that, comprise electrode active material and the coating layer that is arranged on described electrode active material surface, described electrode active material is positive electrode active materials or negative active core-shell material, the material of described coating layer is counted and is comprised by weight: 0.1 ~ 20 part of polymer monomer and 0.1 ~ 50 part of polymer that ethylene glycol derivative forms, 0.1 ~ 10 part of lithium salts, 0.1 ~ 10 part of polymerization initiator and 50 ~ 99.9 parts of plasticizer, described polymer monomer is selected from fluorine-based polymer monomer, ether polymer monomer, one or more in acrylic polymer monomer and vinyl cyanide polymer monomer.
2. a kind of all solid state lithium ion battery compound electrode material as claimed in claim 1, it is characterized in that, described fluorine-based polymer monomer is vinylidene and/or biasfluoroethylene-hexafluoropropylene, ether polymer monomer is oxirane and/or expoxy propane, and acrylic polymer monomer is methyl methacrylate.
3. a kind of all solid state lithium ion battery compound electrode material as claimed in claim 1, it is characterized in that, described ethylene glycol derivative is selected from one or more in ethylene glycol methacrylate, ethylene glycol dimethacrylate, EDIA and glycol diacrylate.
4. a kind of all solid state lithium ion battery compound electrode material as claimed in claim 1, is characterized in that, the material of described coating layer also comprises the additive of 0.1 ~ 30 part, and described additive is selected from nanometer SiO
2, nano-TiO
2, nanometer Al
2o
3, one or more in single-layer carbon nano-tube, multilayer carbon nanotube, zeolite, montmorillonite and molecular sieve ZSM-5.
5. a kind of all solid state lithium ion battery compound electrode material as claimed in claim 1, is characterized in that, the thickness of coating layer is 0.1 ~ 2000nm.、
6. a kind of all solid state lithium ion battery compound electrode material as claimed in claim 1, is characterized in that, described coating layer does not contain electrode active material away from a side of electrode active material.
7. a preparation method for all solid state lithium ion battery compound electrode material, is characterized in that, comprises the following steps:
Count by weight, get 0.1 ~ 20 part of polymer monomer, 0.1 ~ 50 part of ethylene glycol derivative, 0.1 ~ 10 part of lithium salts, 0.1 ~ 10 part of polymerization initiator and 50 ~ 99.9 parts of plasticizer, preparation obtains mixed solution, and described polymer monomer is selected from one or more in fluorine-based polymer monomer, ether polymer monomer, acrylic polymer monomer and vinyl cyanide polymer monomer;
Described mixed solution is blown to spin processes, liquid phase spraying process or print process by method of electrostatic spinning, electricity and be arranged on electrode active material surface, described electrode active material is positive electrode active materials or negative active core-shell material, by legal, the electron beam polymerization method of hot polymerization or polymerizable ultraviolet method, at described electrode active material surface aggregate, generate coating layer subsequently, make all solid state lithium ion battery compound electrode material.
8. the preparation method of a kind of all solid state lithium ion battery compound electrode material as claimed in claim 7, it is characterized in that, described fluorine-based polymer monomer is vinylidene and/or biasfluoroethylene-hexafluoropropylene, ether polymer monomer is oxirane and/or expoxy propane, and acrylic polymer monomer is methyl methacrylate.
9. the preparation method of a kind of all solid state lithium ion battery compound electrode material as claimed in claim 7, it is characterized in that, described ethylene glycol derivative is selected from one or more in ethylene glycol methacrylate, ethylene glycol dimethacrylate, EDIA and glycol diacrylate.
10. an all solid state lithium ion battery, comprises anode electrode, negative electrode and sulfide base solid electrolyte, and described anode electrode or negative electrode comprise all solid state lithium ion battery compound electrode material claimed in claim 1.
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| PCT/CN2013/073503 WO2014044041A1 (en) | 2012-09-18 | 2013-03-29 | Solid-state lithium ion battery composite electrode material, its preparation method and solid-state lithium-ion battery |
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| CN103682354B (en) | 2016-08-10 |
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