[go: up one dir, main page]

CN111129429A - A lithium-rich manganese-based solid-state battery electrode and secondary battery - Google Patents

A lithium-rich manganese-based solid-state battery electrode and secondary battery Download PDF

Info

Publication number
CN111129429A
CN111129429A CN201911421859.9A CN201911421859A CN111129429A CN 111129429 A CN111129429 A CN 111129429A CN 201911421859 A CN201911421859 A CN 201911421859A CN 111129429 A CN111129429 A CN 111129429A
Authority
CN
China
Prior art keywords
lithium
rich manganese
active material
based active
battery electrode
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201911421859.9A
Other languages
Chinese (zh)
Inventor
武兆辉
王建涛
赵尚骞
张安邦
邵泽超
朱秀龙
史碧梦
张莹
卢世刚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Automotive Battery Research Institute Co Ltd
Original Assignee
China Automotive Battery Research Institute Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Automotive Battery Research Institute Co Ltd filed Critical China Automotive Battery Research Institute Co Ltd
Priority to CN201911421859.9A priority Critical patent/CN111129429A/en
Publication of CN111129429A publication Critical patent/CN111129429A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0562—Solid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention provides a lithium-rich manganese-based solid-state battery electrode and a secondary battery, wherein the lithium-rich manganese-based solid-state battery electrode comprises a lithium-rich manganese-based active material and a halide solid-state electrolyte, and the chemical formula of the halide solid-state electrolyte is LiaMXbWherein M is one or more of Al, Ga, In, Sc, Y and La series, X is one or more of F, Cl and Br, a is more than or equal to 0 and less than or equal to 10, and b is more than or equal to 1 and less than or equal to 13. The invention prepares the lithium-rich manganese-based active material and the halide solid electrolyte into the solid battery electrode, can reduce the reaction activity between the lithium-rich manganese-based active material and the contact interface of the electrolyte, and thus can reduce the reaction activity between the lithium-rich manganese-based active material and the contact interface of the electrolyteAnd the side reaction between the lithium-rich manganese-based active material and the electrolyte interface is reduced, which is beneficial to improving the structural stability of the lithium-rich manganese-based active material in the circulation process.

Description

Lithium-rich manganese-based solid-state battery electrode and secondary battery
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a lithium-rich manganese-based solid-state battery electrode and a secondary battery.
Background
With the large-scale application of lithium ion batteries in the field of electric vehicles, the requirements on the energy density and the safety performance of the lithium ion batteries are higher and higher. The electrode material is a key material of the lithium ion battery, improves the specific capacity of the anode and cathode electrode materials, and is an important way for improving the specific energy of the lithium ion battery. The mass ratio of the positive active material in the full battery is usually the highest, and the improvement of the specific capacity of the positive active material to the improvement of the specific energy of the battery is more remarkable. The specific capacity of the conventional common positive active materials LFP, LCO, LMO, Li-NCA and Li-NCM is usually below 200mAh/g, the specific capacity of the lithium-rich manganese-based positive active material can reach as high as 400mAh/g, and the lithium-rich manganese-based positive active material has rich resources and low cost, so the lithium-rich manganese-based positive active material has wide application prospect.
However, most of the currently commercialized lithium ion batteries are based on liquid electrolytes, and the liquid electrolytes contain a large amount of flammable organic solvents, so that a plurality of potential safety hazards exist. And the normal operating voltage range (vs Li) of lithium-rich manganese-based materials+) The electrolyte is operated at high voltage between 2.0V and 4.8V to ensure that the surface activity of the electrolyte is higher, the side reaction with the electrolyte is more violent, the unstable surface structure enables the surface structure of the material to be rearranged, and transition metal ions and oxygen ions in high oxidation state are easier to generate transition metal dissolutionAnd (4) decomposing and separating out oxygen. The interface problem between the lithium-rich manganese-based active material and the electrolyte is not isolated, but is promoted and occurs in a synergistic manner, so that the performance of the material is rapidly degraded.
The development of solid electrolyte-based all-solid and semi-solid batteries reduces the content of organic liquid electrolyte in the batteries, and is an effective way for reducing the safety risk of the batteries. Currently, commonly used solid electrolytes are classified into oxide solid electrolytes, sulfide solid electrolytes, polymer electrolytes, composite electrolytes, and other solid electrolytes according to their structures and compositions. The oxide solid electrolyte has a wider voltage window and higher chemical and electrochemical stability, but has lower ionic conductivity at normal temperature. In addition, oxide electrolytes are generally hard and therefore difficult to process, and are generally manufactured into solid-state batteries with complicated processes and high interfacial resistance. The sulfide electrolyte has higher ionic conductivity than the oxide electrolyte, and in addition, the sulfide electrolyte has good mechanical strength and mechanical flexibility and better processing performance; however, interface reaction is easy to occur between the sulfide electrolyte and active substances (LCO, Li-NMC and the like), the electrochemical window is narrow, and the electrolyte is extremely sensitive to air and has high requirements on preparation and application environments. The polymer electrolyte has good flexibility, is easy to produce and can form a film in a large area; but has poor thermal stability and low oxidation voltage window (<4.0V vs Li+)。
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a lithium-rich manganese-based solid-state battery electrode and a secondary battery.
The invention provides a lithium-rich manganese-based solid-state battery electrode which comprises a lithium-rich manganese-based active material and a halide solid-state electrolyte, wherein the chemical formula of the halide solid-state electrolyte is LiaMXbWherein M is one or more of Al, Ga, In, Sc, Y and La series, X is one or more of F, Cl and Br, a is more than or equal to 0 and less than or equal to 10, and b is more than or equal to 1 and less than or equal to 13.
According to the invention, the lithium-rich manganese-based active material and the halide solid electrolyte are prepared into the solid battery electrode, so that the reaction activity between the lithium-rich manganese-based active material and an electrolyte contact interface (compared with the lithium-rich manganese-based active material and a liquid electrolyte interface) can be reduced, the side reaction between the lithium-rich manganese-based active material and the electrolyte interface is reduced, and the improvement of the structural stability of the lithium-rich manganese-based active material in the circulation process is facilitated.
Further, the halide solid electrolyte is Li3InCl6、Li3YCl6、Li3YBr6、Li3HoCl6、Li3ScCl6One or more of (a).
The halide solid electrolyte can be coated on the surface of the lithium-rich manganese-based active material, or the halide solid electrolyte and the lithium-rich manganese-based active material can be directly and uniformly mixed in a mechanical stirring, ball milling, ultrasonic and other modes.
Further, the weight ratio of the halide solid state electrolyte to the lithium-rich manganese-based active material is (1:99) - (99:1), preferably (5:95) - (50:50), and more preferably (10:90) - (30: 70).
The chemical formula of the lithium-rich manganese-based active material is xLi2MnO3·(1-x)LiMO2Wherein 0 is<x<1, M is one or more of Mn, Ni and Co.
Further, before being coated or mixed with the halide solid electrolyte, the lithium-rich manganese-based active material is also subjected to surface modification coating, and the coating can be simple oxide TiO2、Al2O3、ZrO2、MnO2、MoO3、CeO2Iso, phosphate FePO4、CoPO4、NiPO4Etc. fluoride GaF2、AlF3、SmF3Etc. lithium salt of oxide LiAlO2、LiZrO3、LiTiO3、Li4Ti5O12、Li3VO4、LiNiPO4、LiNbO3And the like, electron good conductors such as simple substances of Al, carbon materials, and the like, and organic high molecular polymers such as Polyaniline (PAN), polyacrylonitrile-butadiene (PAB), and the like.
Further, the coating layer of the lithium-rich manganese-based active material includes one or more of the above substances, but is not limited thereto.
The coating layer can enhance contact between the halide solid electrolyte and the active material, and can also suppress side reactions and interdiffusion between the solid electrolyte and the active material.
Further preferably, the coating layer is an oxide lithium salt LiAlO having excellent ion conductivity2、LiZrO3、LiTiO3、Li4Ti5O12、Li3VO4、LiNiPO4、LiNbO3And the like.
Further, the weight of the coating layer is 0.01-20% of the lithium-rich manganese-based active material, and preferably 1-8%.
Further, before being coated with or mixed with the halide solid-state electrolyte, the lithium-rich manganese-based active material can be modified by element doping, and mainly comprises: na, K and the like are doped at Li position, Fe, Zr, Ti, Zn, Sn, Mo, Al, Cr and the like are doped at transition metal position, F and the like are doped at O position, B and the like are doped in transition metal layer.
Further, the doping of the lithium-rich manganese-based active material includes one or more of the above elements, but is not limited thereto.
The element doping can improve the electronic conductivity or ionic conductivity of the lithium-rich manganese-based active material, and improve the structural stability or multiplying power charge and discharge performance of the lithium-rich manganese-based active material in the circulating process.
Furthermore, the weight of the doping element is 0.001-10%, preferably 0.05-5% of the weight of the lithium-rich manganese-based active material.
Further, the content of the halide solid electrolyte in the electrode of the present invention may be from 1 to 99 wt%, preferably from 5 to 50 wt%, and more preferably from 10 to 30 wt%; the content of the lithium-rich manganese-based active material may be from 1 wt% to 99 wt%, preferably from 50 wt% to 95 wt%, and more preferably from 70 wt% to 90 wt%.
Further, the electrode of the present invention may not contain a conductive agent and a binder, and may also contain a conductive agent and/or a binder, and if contained, the content of the conductive agent may be from 0.5 wt% to 10 wt%, and the content of the binder may be from 0.5 wt% to 10 wt%.
The conductive agent is a conductive agent commonly used in the field of batteries, such as conductive carbon black, carbon nanofiber, carbon nanotube, conductive graphite, graphene and the like; the binder is a binder commonly used in the battery field, such as sodium carboxymethylcellulose (CMC), polyacrylic acid/salt (PAA, PAALi, PPANa), styrene-butadiene rubber (SBR), acrylonitrile multipolymer (LA132, LA133, etc.), sodium alginate (Alg), Chitosan (CS), etc., which can be dispersed in a low-polar solvent, such as an alkane, benzene, ether, etc., polystyrene polymer, polymethyl methacrylate (PMMA), nitrile-butadiene rubber (NBR), styrene-butadiene rubber (SBR), etc.
The invention also provides a secondary battery containing the lithium-rich manganese-based solid battery electrode.
Preferably, the secondary battery is a lithium ion secondary battery including an all-solid battery and a semi-solid battery.
According to the invention, the lithium-rich manganese-based active material and the halide solid electrolyte are prepared into the solid battery electrode, so that the reaction activity between the lithium-rich manganese-based active material and an electrolyte contact interface (compared with the lithium-rich manganese-based active material and a liquid electrolyte interface) can be reduced, the side reaction between the lithium-rich manganese-based active material and the electrolyte interface is reduced, and the improvement of the structural stability of the lithium-rich manganese-based active material in the circulation process is facilitated.
Drawings
Fig. 1 is a first-cycle charge-discharge curve of the all-solid-state battery obtained in example 1 under the charge-discharge test condition with a current density of 100 microamperes;
fig. 2 is a capacity efficiency curve of the all-solid battery obtained in example 1 for the first 120 weeks under the charge and discharge test condition using a current density of 100 microamperes;
fig. 3 is a comparison of the first charge and discharge curves of the all-solid batteries obtained in examples 1 and 4 under the charge and discharge test conditions using a current density of 100 microamperes.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention. The examples do not show the specific techniques or conditions, according to the technical or conditions described in the literature in the field, or according to the product specifications. The reagents or instruments used are conventional products available from regular distributors, not indicated by the manufacturer.
Example 1
This example provides a lithium-rich manganese-based solid state battery electrode comprising 80 wt% lithium-rich manganese-based active material 0.3Li2MnO3·0.7LiNi0.6Co0.2Mn0.2O2And 20% by weight of a halide solid electrolyte Li3InCl6。
The embodiment also provides a preparation method of the electrode, which comprises the following steps: halide electrolyte Li3InCl6With lithium-rich manganese-based active material 0.3Li2MnO3·0.7LiNi0.6Co0.2Mn0.2O2And mixing, wherein the mixing process is carried out in a glove box, and the specific process is that a mortar is adopted for grinding for 20 minutes, and the ground material is used as anode powder.
The present invention also provides a lithium ion secondary battery comprising the above electrode, and the preparation method thereof is as follows: the metal thin indium sheet is used as a negative electrode, and commercial Li is also used as an electrolyte10GeP2S12An electrolyte material. Taking 100 mg of Li10GeP2S12The electrolyte material was placed in a die cell bladder with a cross-sectional area of 0.785 square centimeters and pressed at a pressure of 200 mpa to obtain an electrolyte layer. Then, 10 mg of positive electrode powder was added to one side of the electrolyte layer, and after spreading uniformly, second pressing was performed at a pressure of 350 mpa, and the positive electrode laminate and the electrolyte were laminated together. And then an indium sheet was put on the other side as a negative electrode layer. After the whole process is finished, the inner container is placed into the die battery, the screw is tightly pressed and screwed for sealing, and the all-solid-state secondary battery can be obtained after sealing.
And carrying out a charge-discharge test on the obtained all-solid-state battery by adopting a current density of 100 microamperes, wherein the cut-off voltage is 1.4-4.2V, the charge-discharge curve in the first week is shown in figure 1, and the capacity efficiency curve in the last 120 weeks is shown in figure 2. It can be seen that the lithium-rich manganese-based active material is capable of exerting about 80% of the specific capacity in the liquid battery in the halide solid electrolyte without significant decay over 120 weeks.
Example 2
This example provides a lithium-rich manganese-based solid state battery electrode comprising 70 wt% lithium-rich manganese-based active material 0.3Li2MnO3·0.7LiNi0.6Co0.2Mn0.2O226% by weight of a halide solid electrolyte Li3InCl62 wt% of conductive agent vapor deposition carbon nanotube (VGCF) and 2 wt% of binder Nitrile Butadiene Rubber (NBR).
The embodiment also provides a preparation method of the electrode, which comprises the following steps: 120mg of Li3InCl6Dissolved in 10g of water and 1.4g of 0.3Li were added2MnO3·0.7LiNi0.6Co0.2Mn0.2O2Drying at 100 deg.C, transferring to 200 deg.C vacuum oven for further dehydration drying to obtain Li3InCl6Coated 0.3Li2MnO3·0.7LiNi0.6Co0.2Mn0.2O2(ii) a The whole experimental process does not need inert atmosphere protection. Then 1.52g of lithium-rich manganese-based active material coated by halide electrolyte, 0.4g of halide solid electrolyte, 0.04g of VGCF conductive agent and 0.04g of NBR binder are mixed into n-heptane solvent, the mixture is coated on an aluminum foil with the thickness of 15 microns after being fully stirred uniformly, and the aluminum foil is rolled to 3.0g/cm after being fully dried3And obtaining the electrode.
This example also provides a lithium ion secondary battery comprising the above electrode, prepared substantially in the same manner as in example 1.
Example 3
This example provides a lithium-rich manganese-based solid state battery electrode comprising 80 wt% of a lithium-rich manganese-based active material (0.3 Li)2MnO3·0.7LiNi0.6Co0.2Mn0.2O2Transition metal site doped with Fe in an amount of 3 wt%) and 20 wt% of a halide solid electrolyte Li3InCl6。
The embodiment also provides a preparation method of the electrode, which comprises the following steps: and (3) uniformly mixing the halide solid electrolyte and the doped modified lithium-rich manganese-based active material by mechanical stirring to obtain the anode powder.
This example also provides a lithium ion secondary battery including the above electrode, and the preparation method is the same as example 1.
Example 4
This example provides a lithium-rich manganese-based solid state battery electrode comprising 80 wt% of a lithium-rich manganese-based active material (0.3 Li)2MnO3·0.7LiNi0.6Co0.2Mn0.2O2Surface modification and coating of LiAlO22 wt% coating amount) and 20 wt% of a halide solid electrolyte Li3InCl6。
The embodiment also provides a preparation method of the electrode, which comprises the following steps: and (3) uniformly mixing the halide solid electrolyte and the lithium-rich manganese-based active material with the surface modified with the coating layer by ultrasonic to obtain the anode powder.
This example also provides a lithium ion secondary battery including the above electrode, and the preparation method is the same as example 1.
The first charge-discharge curve of the obtained all-solid-state battery subjected to the charge-discharge test with the current density of 100 microamperes and the comparison graph of the first charge-discharge curve and the example 1 are shown in fig. 3, and it can be seen from the graph that the surface of the obtained all-solid-state battery is coated with LiAlO2Then, the capacity of the lithium-rich manganese-based active material in the halide solid-state electrode is improved.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. The lithium-rich manganese-based solid-state battery electrode is characterized by comprising a lithium-rich manganese-based active materialAnd a halide solid electrolyte having a chemical formula of LiaMXbWherein M is one or more of Al, Ga, In, Sc, Y and La series, X is one or more of F, Cl and Br, a is more than or equal to 0 and less than or equal to 10, and b is more than or equal to 1 and less than or equal to 13.
2. The lithium-rich manganese-based solid state battery electrode of claim 1, wherein the halide solid state electrolyte is Li3InCl6、Li3YCl6、Li3YBr6、Li3HoCl6、Li3ScCl6One or more of (a).
3. The lithium-rich manganese-based solid state battery electrode according to claim 1 or 2, characterized in that the halide solid state electrolyte is coated on the surface of the lithium-rich manganese-based active material;
or the halide solid electrolyte and the lithium-rich manganese-based active material are directly and uniformly mixed.
4. The lithium-rich manganese-based solid state battery electrode according to claim 3, characterized in that the weight ratio of the halide solid state electrolyte to the lithium-rich manganese-based active material is (1:99) - (99:1), preferably (5:95) - (50:50), and more preferably (10:90) - (30: 70).
5. The lithium-rich manganese-based solid state battery electrode of claim 4, wherein the lithium-rich manganese-based active material has a chemical formula of xLi2MnO3·(1-x)LiMO2Wherein 0 is<x<1, M is one or more of Mn, Ni and Co.
6. The lithium-rich manganese-based solid state battery electrode of claim 5, wherein the lithium-rich manganese-based active material is further surface modified with a coating layer comprising the oxide TiO2、Al2O3、ZrO2、MnO2、MoO3、CeO2Phosphate FePO4、CoPO4、NiPO4Of the fluoride GaF2、AlF3、SmF3Lithium salt of oxide LiAlO2、LiZrO3、LiTiO3、Li4Ti5O12、Li3VO4、LiNiPO4、LiNbO3One or more of elementary substance Al, carbon material, organic high polymer polyaniline and polyacrylonitrile-butadiene;
preferably, the coating layer is LiAlO2、LiZrO3、LiTiO3、Li4Ti5O12、Li3VO4、LiNiPO4、LiNbO3One or more of (a).
7. The lithium-rich manganese-based solid state battery electrode of claim 6, wherein the weight of the coating layer is 0.01 to 20%, preferably 1 to 8% of the weight of the lithium-rich manganese-based active material.
8. The lithium-rich manganese-based solid state battery electrode of claim 5, wherein the lithium-rich manganese-based active material is further modified by elemental doping, including doping with Na or K at the Li site, doping with Fe, Zr, Ti, Zn, Sn, Mo, Al or Cr at the transition metal site, doping with F at the O site, and doping with one or more of B at the transition metal layer.
9. The lithium-rich manganese-based solid state battery electrode of claim 8, wherein the doping element is present in an amount of 0.001 to 10%, preferably 0.05 to 5% by weight of the lithium-rich manganese-based active material.
10. A secondary battery comprising the lithium-rich manganese-based solid-state battery electrode according to any one of claims 1 to 9;
preferably, the secondary battery is a lithium ion secondary battery.
CN201911421859.9A 2019-12-31 2019-12-31 A lithium-rich manganese-based solid-state battery electrode and secondary battery Pending CN111129429A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911421859.9A CN111129429A (en) 2019-12-31 2019-12-31 A lithium-rich manganese-based solid-state battery electrode and secondary battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911421859.9A CN111129429A (en) 2019-12-31 2019-12-31 A lithium-rich manganese-based solid-state battery electrode and secondary battery

Publications (1)

Publication Number Publication Date
CN111129429A true CN111129429A (en) 2020-05-08

Family

ID=70507033

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911421859.9A Pending CN111129429A (en) 2019-12-31 2019-12-31 A lithium-rich manganese-based solid-state battery electrode and secondary battery

Country Status (1)

Country Link
CN (1) CN111129429A (en)

Cited By (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111490243A (en) * 2020-05-25 2020-08-04 蜂巢能源科技有限公司 Composite positive electrode material for lithium ion battery, preparation method and application thereof
CN111640979A (en) * 2020-05-19 2020-09-08 国联汽车动力电池研究院有限责任公司 Solid electrolyte and preparation method and application thereof
CN111900461A (en) * 2020-07-17 2020-11-06 国联汽车动力电池研究院有限责任公司 Fluorine-containing solid electrolyte for high-voltage all-solid-state battery and preparation method and application thereof
CN112151798A (en) * 2020-09-16 2020-12-29 天目湖先进储能技术研究院有限公司 Fluoride/oxide co-coated positive electrode material and preparation method thereof
CN112670563A (en) * 2020-12-30 2021-04-16 广东微电新能源有限公司 Solid electrolyte material, preparation method thereof and solid battery
CN113062013A (en) * 2021-03-16 2021-07-02 中南大学 Lithium vanadate with indium-cerium or indium-doped nanofiber structure and preparation method and application thereof
CN113451566A (en) * 2021-06-22 2021-09-28 合肥国轩高科动力能源有限公司 Composite coated positive electrode material and preparation method and application thereof
CN113851647A (en) * 2020-06-28 2021-12-28 宝山钢铁股份有限公司 Solid electrolyte coated cathode for solid battery and preparation method thereof
CN113845140A (en) * 2020-06-28 2021-12-28 宝山钢铁股份有限公司 Fluorine-doped halide solid electrolyte and preparation method thereof
CN113845141A (en) * 2020-06-28 2021-12-28 宝山钢铁股份有限公司 Fluorine-doped halide solid electrolyte, preparation method and lithium battery
CN114300648A (en) * 2021-12-29 2022-04-08 合肥国轩高科动力能源有限公司 Positive pole piece and preparation method thereof, positive pole plate and solid-state battery
CN114335681A (en) * 2021-11-29 2022-04-12 蜂巢能源科技(无锡)有限公司 Inorganic halide solid electrolyte, preparation method thereof, lithium ion battery and application
CN114597401A (en) * 2022-03-07 2022-06-07 中国科学院宁波材料技术与工程研究所 High-capacity molybdenum polysulfide composite positive electrode material, preparation method and application thereof in all-solid-state battery
CN114614094A (en) * 2022-03-28 2022-06-10 杭州瀛拓科技有限公司 Electrolyte and lithium ion battery electrolyte
CN114614081A (en) * 2022-02-22 2022-06-10 银叶元素公司 Solid electrolyte material and application thereof
CN114665097A (en) * 2022-04-20 2022-06-24 蜂巢能源科技股份有限公司 A kind of cobalt-free cathode material and its preparation method and application
CN114772627A (en) * 2022-03-30 2022-07-22 蜂巢能源科技(无锡)有限公司 Dehydration purification method and application of solid electrolyte
CN114864895A (en) * 2022-05-05 2022-08-05 重庆理英新能源科技有限公司 Surface-reconstructed lithium-rich manganese-based positive electrode material and preparation method and application thereof
CN114865100A (en) * 2022-05-20 2022-08-05 西安工业大学 High-performance all-solid-state lithium ion battery with stable structure and preparation method thereof
CN115000397A (en) * 2022-04-19 2022-09-02 中国第一汽车股份有限公司 Solid-state battery anode material, preparation method thereof and solid-state battery anode
CN115207456A (en) * 2022-07-20 2022-10-18 南京航空航天大学 All-solid-state lithium battery and preparation method thereof
CN115332620A (en) * 2022-08-30 2022-11-11 惠州亿纬锂能股份有限公司 Solid electrolyte, preparation method thereof and preparation method of all-solid-state battery
CN115395017A (en) * 2022-09-27 2022-11-25 广州鹏辉能源科技股份有限公司 Lithium ion battery anode material slurry, preparation method thereof, prepared anode and lithium ion battery
CN115411217A (en) * 2021-05-28 2022-11-29 国联汽车动力电池研究院有限责任公司 Positive electrode for all-solid-state battery and all-solid-state battery
CN115799621A (en) * 2022-09-09 2023-03-14 南开大学 Composite halide solid electrolyte membrane and solid battery prepared from same
CN116053438A (en) * 2023-01-05 2023-05-02 中国科学院化学研究所 High-voltage all-solid-state battery positive electrode material, and preparation method and application thereof
CN117059887A (en) * 2023-10-12 2023-11-14 清陶(昆山)能源发展股份有限公司 Preparation method of composite solid electrolyte membrane and lithium ion battery
WO2023245659A1 (en) * 2022-06-24 2023-12-28 宁德时代新能源科技股份有限公司 Positive electrode material and preparation method therefor, secondary battery, and battery module
WO2024073883A1 (en) * 2022-10-08 2024-04-11 宁德时代新能源科技股份有限公司 Positive electrode active material and preparation therefor, positive electrode sheet, and secondary battery
EP4358182A4 (en) * 2022-08-01 2024-10-23 Contemporary Amperex Technology (Hong Kong) Limited MODIFIED LITHIUM-RICH MANGANESE MATERIAL, METHOD FOR MODIFYING LITHIUM-RICH MANGANESE MATERIAL, SECONDARY BATTERY AND ELECTRIC DEVICE
US12176481B2 (en) 2020-11-24 2024-12-24 Samsung Electronics Co., Ltd. Solid ion conductor, solid electrolyte and electrochemical device including the same, and method of preparing the solid ion conductor
CN119480926A (en) * 2024-11-15 2025-02-18 有研(广东)新材料技术研究院 A high voltage resistant thick electrode and preparation method and battery cell
WO2025185701A1 (en) * 2024-03-06 2025-09-12 宁波容百新能源科技股份有限公司 Positive electrode material and preparation method therefor, positive electrode sheet, and all-solid-state battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102569774A (en) * 2010-12-29 2012-07-11 比亚迪股份有限公司 Cathode active material and preparation method thereof, cathode material and lithium ion battery
CN105958008A (en) * 2016-06-30 2016-09-21 深圳博磊达新能源科技有限公司 Composite positive electrode plate of lithium ion battery, preparation method thereof and lithium ion battery
US20170012284A1 (en) * 2015-07-10 2017-01-12 California Institute Of Technology Aluminum borate coated lithium ion cathode materials
WO2019135346A1 (en) * 2018-01-05 2019-07-11 パナソニックＩｐマネジメント株式会社 Positive electrode material and battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102569774A (en) * 2010-12-29 2012-07-11 比亚迪股份有限公司 Cathode active material and preparation method thereof, cathode material and lithium ion battery
US20170012284A1 (en) * 2015-07-10 2017-01-12 California Institute Of Technology Aluminum borate coated lithium ion cathode materials
CN105958008A (en) * 2016-06-30 2016-09-21 深圳博磊达新能源科技有限公司 Composite positive electrode plate of lithium ion battery, preparation method thereof and lithium ion battery
WO2019135346A1 (en) * 2018-01-05 2019-07-11 パナソニックＩｐマネジメント株式会社 Positive electrode material and battery

Cited By (55)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111640979A (en) * 2020-05-19 2020-09-08 国联汽车动力电池研究院有限责任公司 Solid electrolyte and preparation method and application thereof
CN111640979B (en) * 2020-05-19 2021-08-24 国联汽车动力电池研究院有限责任公司 A kind of solid electrolyte and its preparation method and application
JP7389247B2 (en) 2020-05-25 2023-11-29 蜂巣能源科技股▲ふん▼有限公司 Composite positive electrode material for lithium ion batteries, its preparation method and use
JP2023500040A (en) * 2020-05-25 2023-01-04 蜂巣能源科技股▲ふん▼有限公司 Composite cathode material for lithium-ion batteries, method of preparation and use thereof
KR20220150938A (en) * 2020-05-25 2022-11-11 에스볼트 에너지 테크놀러지 컴퍼니 리미티드 Composite cathode material for lithium ion battery, manufacturing method and use thereof
KR102888065B1 (en) 2020-05-25 2025-11-18 에스볼트 에너지 테크놀러지 컴퍼니 리미티드 Composite cathode material for lithium ion batteries, its manufacturing method and use
CN111490243A (en) * 2020-05-25 2020-08-04 蜂巢能源科技有限公司 Composite positive electrode material for lithium ion battery, preparation method and application thereof
CN111490243B (en) * 2020-05-25 2022-03-11 蜂巢能源科技有限公司 Composite positive electrode material for lithium ion battery, preparation method and application thereof
WO2021238152A1 (en) * 2020-05-25 2021-12-02 蜂巢能源科技有限公司 Composite positive electrode material for lithium ion battery, preparation method therefor, and use thereof
CN113851647A (en) * 2020-06-28 2021-12-28 宝山钢铁股份有限公司 Solid electrolyte coated cathode for solid battery and preparation method thereof
CN113845141A (en) * 2020-06-28 2021-12-28 宝山钢铁股份有限公司 Fluorine-doped halide solid electrolyte, preparation method and lithium battery
CN113845140A (en) * 2020-06-28 2021-12-28 宝山钢铁股份有限公司 Fluorine-doped halide solid electrolyte and preparation method thereof
CN111900461B (en) * 2020-07-17 2022-06-28 国联汽车动力电池研究院有限责任公司 Fluorine-containing solid electrolyte for high-voltage all-solid-state battery and preparation method and application thereof
CN111900461A (en) * 2020-07-17 2020-11-06 国联汽车动力电池研究院有限责任公司 Fluorine-containing solid electrolyte for high-voltage all-solid-state battery and preparation method and application thereof
CN112151798B (en) * 2020-09-16 2022-03-15 天目湖先进储能技术研究院有限公司 Fluoride/oxide co-coated positive electrode material and preparation method thereof
CN112151798A (en) * 2020-09-16 2020-12-29 天目湖先进储能技术研究院有限公司 Fluoride/oxide co-coated positive electrode material and preparation method thereof
US12176481B2 (en) 2020-11-24 2024-12-24 Samsung Electronics Co., Ltd. Solid ion conductor, solid electrolyte and electrochemical device including the same, and method of preparing the solid ion conductor
CN112670563B (en) * 2020-12-30 2022-05-17 广东微电新能源有限公司 Solid electrolyte material, preparation method thereof and solid battery
CN112670563A (en) * 2020-12-30 2021-04-16 广东微电新能源有限公司 Solid electrolyte material, preparation method thereof and solid battery
CN113062013B (en) * 2021-03-16 2022-04-12 中南大学 A kind of indium cerium or indium doped nanofiber structure lithium vanadate and its preparation method and application
CN113062013A (en) * 2021-03-16 2021-07-02 中南大学 Lithium vanadate with indium-cerium or indium-doped nanofiber structure and preparation method and application thereof
CN115411217A (en) * 2021-05-28 2022-11-29 国联汽车动力电池研究院有限责任公司 Positive electrode for all-solid-state battery and all-solid-state battery
CN113451566A (en) * 2021-06-22 2021-09-28 合肥国轩高科动力能源有限公司 Composite coated positive electrode material and preparation method and application thereof
CN114335681A (en) * 2021-11-29 2022-04-12 蜂巢能源科技(无锡)有限公司 Inorganic halide solid electrolyte, preparation method thereof, lithium ion battery and application
CN114335681B (en) * 2021-11-29 2023-11-28 蜂巢能源科技(无锡)有限公司 Inorganic halide solid electrolyte, preparation method thereof, lithium ion battery and application
CN114300648A (en) * 2021-12-29 2022-04-08 合肥国轩高科动力能源有限公司 Positive pole piece and preparation method thereof, positive pole plate and solid-state battery
CN114614081A (en) * 2022-02-22 2022-06-10 银叶元素公司 Solid electrolyte material and application thereof
CN114614081B (en) * 2022-02-22 2024-04-05 银叶元素公司 Solid electrolyte material and application thereof
CN114597401A (en) * 2022-03-07 2022-06-07 中国科学院宁波材料技术与工程研究所 High-capacity molybdenum polysulfide composite positive electrode material, preparation method and application thereof in all-solid-state battery
CN114597401B (en) * 2022-03-07 2024-02-06 中国科学院宁波材料技术与工程研究所 High-capacity molybdenum polysulfide composite positive electrode material, preparation method and application thereof in all-solid-state battery
CN114614094A (en) * 2022-03-28 2022-06-10 杭州瀛拓科技有限公司 Electrolyte and lithium ion battery electrolyte
CN114772627B (en) * 2022-03-30 2024-02-13 蜂巢能源科技(无锡)有限公司 Dehydration purification method and application of solid electrolyte
CN114772627A (en) * 2022-03-30 2022-07-22 蜂巢能源科技(无锡)有限公司 Dehydration purification method and application of solid electrolyte
CN115000397A (en) * 2022-04-19 2022-09-02 中国第一汽车股份有限公司 Solid-state battery anode material, preparation method thereof and solid-state battery anode
CN114665097B (en) * 2022-04-20 2024-06-25 蜂巢能源科技股份有限公司 A cobalt-free positive electrode material and its preparation method and application
CN114665097A (en) * 2022-04-20 2022-06-24 蜂巢能源科技股份有限公司 A kind of cobalt-free cathode material and its preparation method and application
CN114864895A (en) * 2022-05-05 2022-08-05 重庆理英新能源科技有限公司 Surface-reconstructed lithium-rich manganese-based positive electrode material and preparation method and application thereof
CN114865100A (en) * 2022-05-20 2022-08-05 西安工业大学 High-performance all-solid-state lithium ion battery with stable structure and preparation method thereof
CN114865100B (en) * 2022-05-20 2025-11-07 西安工业大学 All-solid-state lithium ion battery with stable structure and preparation method thereof
WO2023245659A1 (en) * 2022-06-24 2023-12-28 宁德时代新能源科技股份有限公司 Positive electrode material and preparation method therefor, secondary battery, and battery module
CN115207456A (en) * 2022-07-20 2022-10-18 南京航空航天大学 All-solid-state lithium battery and preparation method thereof
EP4358182A4 (en) * 2022-08-01 2024-10-23 Contemporary Amperex Technology (Hong Kong) Limited MODIFIED LITHIUM-RICH MANGANESE MATERIAL, METHOD FOR MODIFYING LITHIUM-RICH MANGANESE MATERIAL, SECONDARY BATTERY AND ELECTRIC DEVICE
CN115332620A (en) * 2022-08-30 2022-11-11 惠州亿纬锂能股份有限公司 Solid electrolyte, preparation method thereof and preparation method of all-solid-state battery
CN115799621B (en) * 2022-09-09 2024-01-16 南开大学 Composite halide solid electrolyte membrane and solid battery prepared from same
CN115799621A (en) * 2022-09-09 2023-03-14 南开大学 Composite halide solid electrolyte membrane and solid battery prepared from same
CN115395017B (en) * 2022-09-27 2025-03-25 广州鹏辉能源科技股份有限公司 Lithium ion battery positive electrode material slurry and preparation method thereof, prepared positive electrode and lithium ion battery
CN115395017A (en) * 2022-09-27 2022-11-25 广州鹏辉能源科技股份有限公司 Lithium ion battery anode material slurry, preparation method thereof, prepared anode and lithium ion battery
CN118176599A (en) * 2022-10-08 2024-06-11 宁德时代新能源科技股份有限公司 Positive electrode active material and preparation thereof, positive electrode sheet and secondary battery
WO2024073883A1 (en) * 2022-10-08 2024-04-11 宁德时代新能源科技股份有限公司 Positive electrode active material and preparation therefor, positive electrode sheet, and secondary battery
CN118176599B (en) * 2022-10-08 2026-01-30 宁德时代新能源科技股份有限公司 Positive electrode active materials and their preparation, positive electrode sheets and secondary batteries
CN116053438A (en) * 2023-01-05 2023-05-02 中国科学院化学研究所 High-voltage all-solid-state battery positive electrode material, and preparation method and application thereof
CN117059887B (en) * 2023-10-12 2023-12-22 清陶(昆山)能源发展股份有限公司 Preparation method of composite solid electrolyte membrane and lithium ion battery
CN117059887A (en) * 2023-10-12 2023-11-14 清陶(昆山)能源发展股份有限公司 Preparation method of composite solid electrolyte membrane and lithium ion battery
WO2025185701A1 (en) * 2024-03-06 2025-09-12 宁波容百新能源科技股份有限公司 Positive electrode material and preparation method therefor, positive electrode sheet, and all-solid-state battery
CN119480926A (en) * 2024-11-15 2025-02-18 有研(广东)新材料技术研究院 A high voltage resistant thick electrode and preparation method and battery cell

Similar Documents

Publication Publication Date Title
CN111129429A (en) A lithium-rich manganese-based solid-state battery electrode and secondary battery
Tang et al. An aqueous rechargeable lithium battery of excellent rate capability based on a nanocomposite of MoO 3 coated with PPy and LiMn 2 O 4
Chen et al. An investigation of functionalized electrolyte using succinonitrile additive for high voltage lithium-ion batteries
JP2020064866A (en) Aqueous slurry for battery electrodes
Wu et al. Investigations on high energy lithium-ion batteries with aqueous binder
CN108511786B (en) A kind of all-solid-state lithium battery and preparation method thereof
EP3840090A1 (en) Sulfur-based positive electrode active material for use in solid-state battery, preparation for material, and applications thereof
KR20120010552A (en) Solid lithium lithium ion secondary batteries and electrodes that can be used
CN105470475A (en) Cathode active material for lithium battery, lithium battery, and method for producing cathode active material for lithium battery
KR20180094184A (en) All-solid battery using sulfide-based solid electrolyte and method of manufacturing the same
JP2019125481A (en) Negative electrode mixture for all-solid lithium ion secondary battery and manufacturing method thereof
CN102473922A (en) Electrode for battery, battery provided with electrode for battery, and method for manufacturing the electrode for battery
CN117374373A (en) An all-solid-state soft pack battery
CN115863750A (en) A solid-state lithium-ion battery
US9088047B2 (en) Electrode for a lithium battery
JP5110817B2 (en) Non-aqueous electrolyte battery
Zhu et al. Stabilizing high-voltage cathode materials for next-generation Li-ion batteries
CN116154100A (en) Lithium supplementing positive electrode, preparation method thereof and lithium ion secondary battery
KR20120015418A (en) Solid lithium lithium ion secondary batteries and electrodes that can be used
CN110970598A (en) Composite negative electrode of lithium battery, preparation method thereof and lithium battery comprising negative electrode
Chen et al. Improving the performance of soft carbon for lithium-ion batteries
KR101999473B1 (en) Surface coated electrode active material for lithium secondary battery and lithium secondary battery using the same
JP6819533B2 (en) Negative electrode mixture for all-solid-state lithium-ion secondary batteries
US20220037659A1 (en) All solid state battery
KR102782891B1 (en) All solid state battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20200508