CN109004201A - A kind of preparation method and applications of the high-voltage anode material of the nucleocapsid structure suitable for polymer-based solid state electrolyte - Google Patents
A kind of preparation method and applications of the high-voltage anode material of the nucleocapsid structure suitable for polymer-based solid state electrolyte Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- 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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Abstract
The invention discloses a kind of preparation methods of the high-voltage anode material of nucleocapsid structure suitable for polymer-based solid state electrolyte, it is characterized by: the nuclear material with high voltage of the shell material of 0.5-5 mass parts and 100 mass parts is added respectively in the cavity of mechanical coating machine, then the protection inert gases such as gas nitrogen or argon gas are passed through in cavity, start mechanical coating machine, machine is during high-speed cruising, material is squeezed, rubbing action and utilization itself generate heat, so that particle surface generates mechanochemical effect, after 30-60min, shell material is coated on the surface of nuclear material, by the further spheroidization of scanning electron microscopic observation material and after shell material is embedded in nuclear material surface, clad is observed by projection Electronic Speculum, so that the thickness of shell material reaches 20-60nm, height can be obtained Positive polarity material.Advantage is: having the high voltage withstanding material of transmission lithium ion ability to the cladding of high-voltage anode material, it is convenient to operate, can be with large-scale serial production.
Description
Technical field
The present invention relates to field of new energy technologies, more particularly to a kind of core-suitable for polymer-based solid state electrolyte
The preparation method of the high-voltage anode material of shell structure further relates to a kind of positive electrode of nucleocapsid structure in high voltage polymer
Application in solid state lithium battery.
Background technique
Since solid state lithium battery does not have the electrolyte of free state, the combustibility of battery is greatly reduced, battery is improved
Safety.Compared to liquid lithium ionic cell, solid state lithium battery has the performances such as higher energy density, better cycle life.
Solid state lithium battery can be divided into polymer solid lithium battery and inorganic solid-state lithium battery.Wherein polymer solid lithium battery has volume
To volume production, Flexible Manufacture characteristic, it can be made into hull cell and flexible battery, can be applied to intelligent wearing, ultra micro intelligent ultrathin
Apparatus field, therefore it has been sent to great expectations.
In polymer solid lithium ion battery, solid polyelectrolyte has light weight, Yi Cheng as core material
Film, highly-safe, the advantages that stabilization to lithium, common polymer substrate includes polyethers, polyester and polyamine and its and polysilane
Or the polymer of poly- phosphide etc..But these polymer often have lower conductivity at room temperature and relatively narrow electrochemistry
Window, so that application of the solid polyelectrolyte solid electrolyte in high-voltage anode material system is restricted.
201710951551.X patent discloses a kind of composite solid electrolyte of polymer-ceramic-polymeric multilayer structure,
201710040922.9 patent disclose polymer, lithium salts, organic matter doping composite solid electrolyte, 201710829019.0
Patent discloses a kind of cured semi-interpenetrating polymer solid electrolyte of ultraviolet light, and 201510258846.X patent discloses one kind
Polymer, boron cage modle anion lithium salts, dopant composite solid electrolyte, these polymer-based solid state electrolyte all have higher
Ionic conductivity and wider electrochemical window, but in practical applications, these polymer materials inevitably with height electricity
The positive electrode of pressure contacts, so that polymer resolves into small-molecule substance, deterioration of cell properties.
Summary of the invention
The purpose of the present invention is: in view of the above deficiencies, provide a kind of core-shell structure copolymer knot suitable for polymer-based solid state electrolyte
The preparation method and applications of the high-voltage anode material of structure.
In order to achieve the above objectives, the technical solution adopted by the present invention is that:
A kind of preparation method of the high-voltage anode material of the nucleocapsid structure suitable for polymer-based solid state electrolyte, point
The nuclear material with high voltage of the shell material of 0.5-5 mass parts and 100 mass parts is not added in the cavity of mechanical coating machine,
Then it is passed through the protection inert gases such as gas nitrogen or argon gas in cavity, starts mechanical coating machine, machine is in high-speed cruising process
In, material is squeezed, rubbing action and utilization itself generate heat, so that particle surface generates mechanochemical effect, 30-
After 60min, shell material is coated on the surface of nuclear material, and by the further spheroidization of scanning electron microscopic observation material and shell material is inlayed
Behind nuclear material surface, observing clad by projection Electronic Speculum can be obtained height so that the thickness of shell material reaches 20-60nm
Positive polarity material.
The nucleocapsid structure of the high-voltage anode material, shell structure are one layer of structure or multilayered structure.
The shell structure is Li1+xAlxTi2-x(PO4)3(LATP), Li7-xLa3Zr2-xMxO12(M=Ta, Nb) (0 ﹤ x ﹤ 2)
(LLZMO), LixLa2/3-xTiO3(LLTO), LiAlO2(LAO), Li2ZrO3(LZO), Li4Ti5O12(LTO)。
The nuclear structure is LiNiPO (LiMnxFe(1-x)PO4), cobalt phosphate lithium (LiCoPO4), LiNiPO
(LiNiPO4), LiMn2O4 (LiMnO4), nickel ion doped (LiNi0.5Mn1.5O4), ternary material (LiNixCoyMnzO2), rich manganese lithium
Material xLi2MnO3﹒ (1-x) LiMO2(M=Ni, Co, Mn).
A kind of application of the positive electrode of nucleocapsid structure in high voltage polymer solid lithium battery, including anode composite,
Solid polyelectrolyte and lithium anode, using lithium metal as cathode, upper superposition solid polyelectrolyte and multiple
It closes anode and is assembled into solid state lithium battery, battery charging and discharging ends electricity 3.0-4.3V.
The anode composite includes the positive electrode of the shell-core structure of 75-90 mass parts, the conductive agent of 1-5 mass parts, 1-
The binder of 5 mass parts, the polymer material of 5-15 mass parts and the lithium salts of 3-8 mass parts；Uniformly divided by mechanical stirring
It is dispersed among NMP, obtains anode composite slurry, then on a current collector with coating, obtained by drying, roll-in, cutting compound
Positive plate.
The solid polyelectrolyte includes polymer material, lithium salts and ceramic powder.
The polymer material include polyether material, polyacrylate material, polyacrylonitrile material, in polyphenyl thioether material
One or more.
Further, conductive agent includes that carbon black (AB), SPUER-P, KS-6, electrically conductive graphite, carbon fiber (VGCF), carbon are received
Mitron (CNT), graphene.
Further, adhesive is Pluronic F-127 (PEO), Kynoar (PVDF), (Kynoar-hexafluoro third
Alkene) copolymer (PVDF-HFP), poly- ethylene carbonate (PEC), polytrimethylene carbonate (PTMC), polypropylene carbonate
(PPC) one such or several.
Further, lithium salts includes lithium perchlorate (LiClO4), hexafluoroarsenate lithium (LiAsF6), LiBF4
(LiBF4), lithium hexafluoro phosphate (LiPF6), trifluoromethyl sulfonic acid lithium (LiCF3SO3), bis- (trifluoromethane sulfonic acid) imine lithiums
(LiTFSI), three (trifluoromethane sulfonic acid) lithium methide (LiC (CF3SO2)3), di-oxalate lithium borate (LiBOB).
Further, polymer material is polymethyl methacrylate, polyether silane, epichlorohydrin rubber and perfluoropolyether.
Further, ceramic powder is lithium lanthanum zirconium oxygen (LLZO), lithium lanthanum zirconium tantalum oxygen (LLZTO), Li-La-Ti oxygen (LLTO), oxygen
Change aluminium (Al2O3), zirconium oxide (ZrO2), titanium oxide (TiO2), barium sulfate (BaSO4)。
Compared with prior art, achieved to have the technical effect that the present invention designs a kind of with nucleocapsid structure by the present invention
High-voltage anode material coats a thin layer of high voltage withstanding inorganic solid electrolyte material on high-voltage anode material surface
Or multilayer inorganic material is coated on high-voltage anode material surface, but outermost layer is inorganic solid electrolyte material；Multiple
It closes in anode, the solid state lithium battery tool that directly contacts, while assembling of the polymer material with positive electrode can be effectively avoided
There are good interface compatibility and stable cycle performance；With transmission lithium ion ability high voltage withstanding material to high voltage just
The cladding of pole material, it is convenient to operate, can be with large-scale serial production, while high-voltage anode material being made to can be used for polymer
Solid state lithium battery field, and there is the polymer solid battery assembled stable circulation and higher capacity to play.
Detailed description of the invention
Fig. 1 is the LiNi of LLZMO claddingxCoyMnzO2SEM figure.
Fig. 2 is the LiNi of LATP cladding0.5Mn1.5O4TEM figure.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and embodiments:
Embodiment one:
The high-voltage anode of a kind of nucleocapsid structure suitable for polymer-based solid state electrolyte of the invention as shown in Figure 1:
The preparation method of material, respectively by the Li of the 150nm of 2 mass parts7-xLa3Zr2-xMxO12(M=Ta, Nb) (0 ﹤ x ﹤ 2) (LLZMO)
With the ternary material (LiNi with high voltage of 100 mass partsxCoyMnzO2) be added in the cavity of mechanical coating machine, then exist
It is passed through the protection inert gases such as gas nitrogen or argon gas in cavity, starts mechanical coating machine, machine is during high-speed cruising, material
It is squeezed, rubbing action and generates heat using itself, so that particle surface generates mechanochemical effect, after 40min, shell
Material is coated on the surface of nuclear material, and by the further spheroidization of scanning electron microscopic observation material and shell material is embedded in nuclear material table
Behind face, observing clad by projection Electronic Speculum can be obtained high-voltage anode material so that the thickness of shell material reaches 20nm.
A kind of application of the positive electrode of nucleocapsid structure in high voltage polymer solid lithium battery, including anode composite,
Solid polyelectrolyte and lithium anode, using lithium metal as cathode, upper superposition solid polyelectrolyte and multiple
It closes anode and is assembled into solid state lithium battery, battery charging and discharging ends electricity 3.0-4.3V.
Wherein, the anode composite includes the positive electrode of the shell-core structure of 80 mass parts, the conductive agent stone of 2 mass parts
Black alkene, the binder polypropylene carbonate (PPC) of 3 mass parts, the polymer material perfluoropolyether and 5 mass parts of 10 mass parts
Lithium salts LiBF4 (LiBF4)；It is dispersed among NMP by mechanical stirring, obtains anode composite slurry, then use
Coating on a current collector, obtains anode composite piece by drying, roll-in, cutting.
The solid polyelectrolyte includes polymer material polymethyl methacrylate, lithium salts LiBF4
(LiBF4) and ceramic powder lithium lanthanum zirconium oxygen (LLZO), mass ratio are as follows: 60:30:10.
Above-mentioned contrast groups anode composite: Li7-xLa3Zr2-xMxO12It is (M=Ta, Nb) (0 ﹤ x ﹤ 2) (LLZMO), uncoated
Ternary material (LiNixCoyMnzO2), conductive agent graphene, binder polypropylene carbonate (PPC), polymer material perfluor it is poly-
Ether, lithium salts LiBF4 (LiBF4) mass ratio are as follows: 2:78:2:3:10:5.
Embodiment two:
It is as illustrated in fig. 1 and 2: a kind of high voltage of nucleocapsid structure suitable for polymer-based solid state electrolyte of the invention
The preparation method of positive electrode, respectively by the LixLa of the 400nm of 4 mass parts2/3-xTiO3(LLTO) have with 100 mass parts
LiNiPO (the LiMn of high voltagexFe(1-x)PO4) be added in the cavity of mechanical coating machine, protection gas is then passed through in cavity
The inert gases such as nitrogen or argon gas start mechanical coating machine, and during high-speed cruising, material is squeezed machine, friction is made
Heat is generated with and using itself, so that particle surface generates mechanochemical effect, after 60min, LixLa2/3-xTiO3
(LLTO) it is coated on LiNiPO (LiMnxFe(1-x)PO4) surface, by the further spheroidization of scanning electron microscopic observation material and
After shell material is embedded in nuclear material surface, clad is observed by projection Electronic Speculum, so that the thickness of shell material reaches 23nm
Obtain high-voltage anode material.
A kind of application of the positive electrode of nucleocapsid structure in high voltage polymer solid lithium battery, including anode composite,
Solid polyelectrolyte and lithium anode, using lithium metal as cathode, upper superposition solid polyelectrolyte and multiple
It closes anode and is assembled into solid state lithium battery, battery charging and discharging ends electricity 3.0-4.3V.
Wherein, the anode composite includes the positive electrode of the shell-core structure of 75 mass parts, the conductive agent carbon of 2 mass parts
Nanotube (CNT), the binder Pluronic F-127 (PEO) of 3 mass parts, the polymer material epichlorohydrin rubber of 12 mass parts and 8
Bis- (trifluoromethane sulfonic acid) imine lithiums (LiTFSI) of the lithium salts of mass parts；It is dispersed among NMP, is obtained by mechanical stirring
Then on a current collector with coating anode composite slurry obtains anode composite piece by drying, roll-in, cutting.
The solid polyelectrolyte includes polymer material epichlorohydrin rubber, bis- (trifluoromethane sulfonic acid) imine lithiums of lithium salts
(LiTFSI) and ceramic powder lithium lanthanum zirconium tantalum oxygen (LLZTO), mass ratio are as follows: 60:35:5.
Above-mentioned contrast groups anode composite: LixLa2/3-xTiO3(LLTO), uncoated LiNiPO (LiMnxFe(1-x)
PO4), conductive agent carbon nanotube (CNT), binder Pluronic F-127 (PEO), polymer material epichlorohydrin rubber, the bis- (trifluoros of lithium salts
Methane sulfonic acid) imine lithium (LiTFSI) are as follows: 4:71:2:3:12:8.
Embodiment three:
It is as illustrated in fig. 1 and 2: a kind of high voltage of nucleocapsid structure suitable for polymer-based solid state electrolyte of the invention
The preparation method of positive electrode, respectively by the Li of the 100nm of 1.5 mass parts1+xAlxTi2-x(PO4)3(LATP) and 100 mass parts
The nickel ion doped (LiNi with high voltage0.5Mn1.5O4) be added in the cavity of mechanical coating machine, guarantor is then passed through in cavity
The inert gases such as gas nitrogen or argon gas are protected, start mechanical coating machine, during high-speed cruising, material is squeezed, rubs machine
Wiping effect and heat is generated using itself, so that particle surface generates mechanochemical effect, after 30min, Li1+xAlxTi2-x
(PO4)3(LATP) it is coated on nickel ion doped (LiNi0.5Mn1.5O4) surface, it is further spherical by scanning electron microscopic observation material
After change and shell material are embedded in nuclear material surface, clad is observed by projection Electronic Speculum, so that the thickness of shell material reaches 26nm,
High-voltage anode material can be obtained.
A kind of application of the positive electrode of nucleocapsid structure in high voltage polymer solid lithium battery, including anode composite,
Solid polyelectrolyte and lithium anode, using lithium metal as cathode, upper superposition solid polyelectrolyte and multiple
It closes anode and is assembled into solid state lithium battery, battery charging and discharging ends electricity 3.0-4.3V.
Wherein, the anode composite includes the positive electrode of the shell-core structure of 83 mass parts, the conductive agent of 1.5 mass parts
Carbon fiber (VGCF), the binder Kynoar (PVDF) of 1.5 mass parts, the polymer material polyether silanes of 9 mass parts with
And 5 mass parts lithium salts lithium hexafluoro phosphate (LiPF6)；It is dispersed among NMP by mechanical stirring, obtains anode composite slurry
Then on a current collector with coating material obtains anode composite piece by drying, roll-in, cutting.
The solid polyelectrolyte includes polymer material polyether silane, lithium salts lithium hexafluoro phosphate (LiPF6) and
Ceramic powder lithium lanthanum zirconium oxygen (LLZO), mass ratio are as follows: 55:30:15.
Above-mentioned contrast groups anode composite: Li1+xAlxTi2-x(PO4)3(LATP), uncoated nickel ion doped
(LiNi0.5Mn1.5O4), conductive agent carbon fiber (VGCF), binder Kynoar (PVDF), polymer material polyether silane,
Lithium salts lithium hexafluoro phosphate (LiPF6) are as follows: 1.5:81.5:1.5:1.5:9:5.
Example IV:
It is as illustrated in fig. 1 and 2: a kind of high voltage of nucleocapsid structure suitable for polymer-based solid state electrolyte of the invention
The preparation method of positive electrode, respectively by the LiNi of the 300nm of 4 mass parts1/3Co1/3Mn1/3O2With 100 mass parts
LiNi0.8Co0.1Mn0.1O2It is added in the cavity of mechanical coating machine, protection nitrogen is then passed through in cavity, start mechanical cladding
After machine 40min, obtains surface and coat LiNi1/3Co1/3Mn1/3O2LiNi0.8Co0.1Mn0.1O2, then respectively by 2 mass parts
The LixLa of 150nm2/3-xTiO3(LLTO) and 100 mass of surface coat LiNi1/3Co1/3Mn1/3O2's
LiNi0.8Co0.1Mn0.1O2, pass through scanning electron microscopic observation material, LiNi0.8Co0.1Mn0.1O2Further spheroidization and LixLa2/3- xTiO3(LLTO) it is embedded in LiNi0.8Co0.1Mn0.1O2Behind surface, clad is observed by projection Electronic Speculum, so that the thickness of shell material
Degree reaches 50-60nm, preferably 55, and high-voltage anode material can be obtained.
A kind of application of the positive electrode of nucleocapsid structure in high voltage polymer solid lithium battery, including anode composite,
Solid polyelectrolyte and lithium anode, using lithium metal as cathode, upper superposition solid polyelectrolyte and multiple
It closes anode and is assembled into solid state lithium battery, battery charging and discharging ends electricity 3.0-4.3V.
Wherein, the anode composite includes the positive electrode of the shell-core structure of the secondary cladding of 80 mass parts, 1.5 mass
The polymer material of the conductive agent electrically conductive graphite of part, the poly- ethylene carbonate of the binder of 1.5 mass parts (PEC), 10 mass parts is poly-
Lithium salts trifluoromethyl sulfonic acid lithium (the LiCF of methyl methacrylate and 7 mass parts3SO3)；It is dispersed in by mechanical stirring
Among NMP, anode composite slurry is obtained, then on a current collector with coating, obtains anode composite by drying, roll-in, cutting
Piece.
The solid polyelectrolyte includes polymer material polymethyl methacrylate, lithium salts trifluoromethyl sulfonic acid lithium
(LiCF3SO3) and ceramic powder aluminium oxide (Al2O3), mass ratio are as follows: 55:35:10.
Above-mentioned contrast groups anode composite: LixLa2/3-xTiO3(LLTO), the LiNi once coated0.8Co0.1Mn0.1O2, lead
Electric agent electrically conductive graphite, the poly- ethylene carbonate of binder (PEC), polymer material polymethyl methacrylate, lithium salts trifluoromethyl
Sulfonic Lithium (LiCF3SO3) are as follows: 2:78:1.5:1.5:10:7.
According to the specific discharge capacity of embodiment one the 1st circle and the 50th circle of experimental group and control group into example IV
(mAh/g) table of comparisons:
Compared with prior art, achieved to have the technical effect that the present invention designs a kind of with nucleocapsid structure by the present invention
High-voltage anode material coats a thin layer of high voltage withstanding inorganic solid electrolyte material on high-voltage anode material surface
Or multilayer inorganic material is coated on high-voltage anode material surface, but outermost layer is inorganic solid electrolyte material；Multiple
It closes in anode, the solid state lithium battery tool that directly contacts, while assembling of the polymer material with positive electrode can be effectively avoided
There are good interface compatibility and stable cycle performance；With transmission lithium ion ability high voltage withstanding material to high voltage just
The cladding of pole material, it is convenient to operate, can be with large-scale serial production, while high-voltage anode material being made to can be used for polymer
Solid state lithium battery field, and there is the polymer solid battery assembled stable circulation and higher capacity to play.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar cans understand the content of the present invention and implement it accordingly, and it is not intended to limit the scope of the present invention.It is all according to the present invention
Equivalent change or modification made by Spirit Essence, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of preparation method of the high-voltage anode material of the nucleocapsid structure suitable for polymer-based solid state electrolyte, special
Sign is: mechanical coating machine is added in the nuclear material with high voltage of the shell material of 0.5-5 mass parts and 100 mass parts respectively
Cavity in, the protection inert gases such as gas nitrogen or argon gas are then passed through in cavity, start mechanical coating machine, machine is in high speed
In operational process, material is squeezed, rubbing action and utilization itself generate heat, so that particle surface generates mechanochemistry
Effect, after 30-60min, shell material is coated on the surface of nuclear material, passes through the further spheroidization of scanning electron microscopic observation material and shell
After material is embedded in nuclear material surface, clad is observed by projection Electronic Speculum, so that the thickness of shell material reaches 20-60nm, i.e.,
High-voltage anode material can be obtained.
2. a kind of high-voltage anode of nucleocapsid structure suitable for polymer-based solid state electrolyte according to claim 1
The preparation method of material, it is characterised in that: the nucleocapsid structure of the high-voltage anode material, shell structure are one layer of structure or more
Layer structure.
3. a kind of high-voltage anode of nucleocapsid structure suitable for polymer-based solid state electrolyte according to claim 1
The preparation method of material, it is characterised in that: the shell structure is Li1+xAlxTi2-x(PO4)3(LATP), Li7-xLa3Zr2-xMxO12
(M=Ta, Nb) (0 ﹤ x ﹤ 2) (LLZMO), LixLa2/3-xTiO3(LLTO), LiAlO2(LAO), Li2ZrO3(LZO), Li4Ti5O12
(LTO)。
4. a kind of high-voltage anode of nucleocapsid structure suitable for polymer-based solid state electrolyte according to claim 1
The preparation method of material, it is characterised in that: the nuclear structure is LiNiPO (LiMnxFe(1-x)PO4), cobalt phosphate lithium
(LiCoPO4), LiNiPO (LiNiPO4), LiMn2O4 (LiMnO4), nickel ion doped (LiNi0.5Mn1.5O4), ternary material
(LiNixCoyMnzO2), rich manganese lithium material xLi2MnO3﹒ (1-x) LiMO2(M=Ni, Co, Mn).
5. a kind of application of positive electrode of nucleocapsid structure in high voltage polymer solid lithium battery, it is characterised in that: including
Anode composite, solid polyelectrolyte and lithium anode, using lithium metal as cathode, upper superposition polymer solid electrolysis
Matter and anode composite are assembled into solid state lithium battery, and battery charging and discharging ends electricity 3.0-4.3V.
6. a kind of positive electrode of nucleocapsid structure according to claim 5 is in high voltage polymer solid lithium battery
Using, it is characterised in that: the anode composite includes the positive electrode of the shell-core structure of 75-90 mass parts, 1-5 mass parts
Conductive agent, the binder of 1-5 mass parts, the polymer material of 5-15 mass parts and the lithium salts of 3-8 mass parts；It is stirred by machinery
It mixes and is dispersed among NMP, obtain anode composite slurry, then on a current collector with coating, by drying, roll-in, cutting
Obtain anode composite piece.
7. a kind of positive electrode of nucleocapsid structure according to claim 5 is in high voltage polymer solid lithium battery
Using, it is characterised in that: the solid polyelectrolyte includes polymer material, lithium salts and ceramic powder.
8. a kind of positive electrode of nucleocapsid structure according to claim 6 or 7 is in high voltage polymer solid lithium battery
Application, it is characterised in that: the polymer material includes polyether material, polyacrylate material, polyacrylonitrile material, polyphenyl
One or more of sulfide material.
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| CN201810860878.0A CN109004201B (en) | 2018-07-30 | 2018-07-30 | Preparation method and application of core-shell structured high-voltage positive electrode material suitable for polymer-based solid electrolyte |
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| CN201810860878.0A CN109004201B (en) | 2018-07-30 | 2018-07-30 | Preparation method and application of core-shell structured high-voltage positive electrode material suitable for polymer-based solid electrolyte |
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| CN109004201B CN109004201B (en) | 2022-01-04 |
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| CN110085805A (en) * | 2019-04-30 | 2019-08-02 | 国联汽车动力电池研究院有限责任公司 | A kind of anode composite and its application in solid polymer lithium ion battery |
| CN110137443A (en) * | 2019-03-18 | 2019-08-16 | 宁德新能源科技有限公司 | Positive electrode and electrochemical appliance comprising the positive electrode |
| CN110148728A (en) * | 2019-05-24 | 2019-08-20 | 隆能科技(南通)有限公司 | A kind of ternary material and preparation method thereof of surface cladding LLTO |
| CN112467116A (en) * | 2020-11-30 | 2021-03-09 | 湖南中科星城石墨有限公司 | Graphite coating material, preparation method thereof and battery cathode |
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| US11539046B2 (en) | 2019-12-27 | 2022-12-27 | Industrial Technology Research Institute | Ion-conducting material, core-shell structure containing the same, electrode prepared with the core-shell structure and metal-ion battery employing the electrode |
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| CN109755512A (en) * | 2018-12-25 | 2019-05-14 | 北京当升材料科技股份有限公司 | A kind of nickelic long-life multielement positive electrode and preparation method thereof |
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| US11539046B2 (en) | 2019-12-27 | 2022-12-27 | Industrial Technology Research Institute | Ion-conducting material, core-shell structure containing the same, electrode prepared with the core-shell structure and metal-ion battery employing the electrode |
| EP4002519A1 (en) | 2020-11-11 | 2022-05-25 | Evonik Operations GmbH | Transition metal oxide particles encapsulated in nanostructured lithium titanate or lithium aluminate, and the use thereof in lithium ion batteries |
| CN112467116A (en) * | 2020-11-30 | 2021-03-09 | 湖南中科星城石墨有限公司 | Graphite coating material, preparation method thereof and battery cathode |
| CN114944488A (en) * | 2022-05-23 | 2022-08-26 | 浙江锂威能源科技有限公司 | Preparation method of coated positive electrode material, product and application thereof |
| CN114944488B (en) * | 2022-05-23 | 2024-02-09 | 浙江锂威能源科技有限公司 | Preparation method of coated positive electrode material, product and application thereof |
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