CN114864872A - Composite electrode and preparation method and application thereof - Google Patents

Composite electrode and preparation method and application thereof Download PDF

Info

Publication number
CN114864872A
CN114864872A CN202210396657.9A CN202210396657A CN114864872A CN 114864872 A CN114864872 A CN 114864872A CN 202210396657 A CN202210396657 A CN 202210396657A CN 114864872 A CN114864872 A CN 114864872A
Authority
CN
China
Prior art keywords
carbon
composite material
composite
coated
equal
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
CN202210396657.9A
Other languages
Chinese (zh)
Inventor
苏威同
成小康
田冰冰
李真棠
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.)
Guangdong Carriage Power Technology Co ltd
Original Assignee
Guangdong Carriage Power Technology 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 Guangdong Carriage Power Technology Co ltd filed Critical Guangdong Carriage Power Technology Co ltd
Priority to CN202210396657.9A priority Critical patent/CN114864872A/en
Publication of CN114864872A publication Critical patent/CN114864872A/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
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/043—Processes of manufacture in general involving compressing or compaction
    • H01M4/0435—Rolling or calendering
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Secondary Cells (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a composite electrode and a preparation method and application thereof, wherein the preparation method comprises the following steps: carrying out carbon coating treatment on the inorganic solid electrolyte to prepare a carbon-coated inorganic solid electrolyte composite material; mixing the carbon-coated inorganic solid electrolyte composite material, an electrode active material and a conductive agent to obtain a premix; adding a binder and an organic solvent into the premix and mixing to obtain slurry; and coating the slurry on a metal foil, drying, and then carrying out cold pressing and flaking treatment to obtain the composite electrode. The inorganic solid electrolyte is firstly subjected to carbon coating treatment, so that the prepared carbon-coated inorganic solid electrolyte composite material has ionic conductivity and electronic conductivity, and then the carbon-coated inorganic solid electrolyte composite material is mixed with an electrode active material to prepare a composite electrode; the composite electrode is used for preparing the semi-solid battery, so that the safety performance of the battery can be improved, and the multiplying power and the cycle performance of the battery can be effectively improved.

Description

Composite electrode and preparation method and application thereof
Technical Field
The invention relates to the technical field of battery electrodes, in particular to a composite electrode and a preparation method and application thereof.
Background
At present, the lithium battery shows wide application prospects in the fields of electric automobiles, hybrid electric vehicles, smart power grids and the like. However, the conventional liquid lithium battery has low energy density and contains a large amount of flammable and combustible organic electrolyte, which makes the battery very challenging in terms of safety performance. The solid-state battery is used as a new generation lithium battery, so that the safety performance of the battery is greatly improved, the use of a diaphragm is reduced, and the energy density of the battery is greatly improved.
Solid electrolytes with application prospects currently have three main directions: inorganic sulfide solid electrolytes, inorganic oxide solid electrolytes, and polymer solid electrolytes. In the conventional oxide solid-state battery, an untreated oxide is directly mixed with an active material and a conductive binder when a composite electrode is manufactured. Although the ionic conductivity of the electrode is improved to a certain extent, the electronic conductivity of the oxide is poor, so that the impedance of the electrode is increased, and the battery multiplying power, the cycle performance and the like are greatly improved.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a composite electrode, and a preparation method and application thereof, and aims to solve the problem that the existing electrode is poor in electronic conductivity, so that the battery rate and the cycle performance are poor.
The technical scheme of the invention is as follows:
a method of making a composite electrode, comprising the steps of:
carrying out carbon coating treatment on the inorganic solid electrolyte to prepare a carbon-coated inorganic solid electrolyte composite material;
mixing the carbon-coated inorganic solid electrolyte composite material with an electrode active material and a conductive agent to obtain a premix;
adding a binder and an organic solvent into the premix and mixing to obtain slurry;
and coating the slurry on a metal foil, drying, and then carrying out cold pressing and flaking treatment to obtain the composite electrode.
The preparation method of the composite electrode comprises the step of preparing a carbon-coated inorganic solid electrolyte composite material, wherein the carbon-coated inorganic solid electrolyte composite material is one or more of a carbon-coated NASICON structure composite material, a carbon-coated perovskite structure composite material, a carbon-coated anti-perovskite structure composite material, a carbon-coated LICCON structure composite material and a carbon-coated garnet structure composite material.
The preparation method of the composite electrode comprises the step of preparing the carbon-coated NASICON structure material by Li 1+a Al a Ge 2-a (PO 4 ) 30 /C composite material or isomorphous heteroatom doped compound thereof, and Li 1+b Al b Ti 2-b (PO 4 ) 3 The material is one or more of a/C composite material or an isoatomic doped compound in the same crystal form, wherein a is more than or equal to 0 and less than or equal to 0.75, and b is more than or equal to 0 and less than or equal to 0.5; and/or the carbon-coated perovskite structure composite material comprises Li 3c La 2/3-c TiO 3 /C composite material or isomorphous heteroatom doped compound thereof, and Li 3/ 8 Sr 7/16 Ta 3/4 Hf 1/4 O 3 /C composite material or isomorphous heteroatom doped compound thereof, and Li 2d-e Sr 1-d Ta e Zr 1-e O 3 The material is one or more of an/C composite material or an isomorphous heteroatom doped compound thereof, wherein C is more than or equal to 0.06 and less than or equal to 0.14, e is more than or equal to 0 and less than or equal to 0.75, and d is 0.75 e; and/or the carbon-coated anti-perovskite structure composite material comprises Li 3-2z M z Ha l O/C composite material and Li 3 OC/C composite material or isomorphous heteroplasmon thereofAny one or more of sub-doping compounds, wherein z is more than or equal to 0 and less than or equal to 0.01, and M comprises Mg 2+ 、Ca 2+ 、Sr 2+ Or Ba 2+ One or more of cations, the Ha l Is element Cl or I; and/or the carbon-coated LISICON structural composite material comprises Li 4-f Si 1-f P f O 4 /C composite material or isomorphous heteroatom doped compound thereof, and Li 14 ZnGe 4 O 16 the/C composite material or one or more of isomorphous heteroatom doped compounds thereof, wherein f is more than or equal to 0.5 and less than or equal to 0.6; and/or the carbon-coated garnet structure composite material comprises Li 7-g La 3 Zr 2-g O 12 the/C composite material or the isomorphous heteroatom doped compound thereof has the g being more than or equal to 0 and less than or equal to 1.
The preparation method of the composite electrode is characterized in that the particle size D50 of the inorganic solid electrolyte in the carbon-coated inorganic solid electrolyte composite material is 0.1-100 mu m.
The preparation method of the composite electrode comprises the step of preparing a composite electrode, wherein the electrode active material is a positive electrode active material or a negative electrode active material, and the positive electrode active material is LiCoO 2 、LiNiO 2 、LiMnO 2 、LiNi 0.5 Mn 1.5 O 4 、LiNi x Co 1-x O 2 、LiNi x Co y Mn 1-x-y O 2 And LiNi x Co y Al 1-x-y O 2 Wherein, 0<x<1，0<y<1，0<x+y<1; the negative active material is hard carbon, graphite, silicon carbon, SiO x And Li 4 Ti 5 O 12 One or more of (a).
The preparation method of the composite electrode comprises the step of preparing the carbon-coated inorganic solid electrolyte composite material, wherein the carbon-coated inorganic solid electrolyte composite material accounts for 0.1-50% of the total mass of the electrode active material and the carbon-coated inorganic solid electrolyte composite material.
The composite electrode is prepared by the preparation method of the composite electrode.
The invention relates to application of a composite electrode, wherein the composite electrode is used for preparing a semi-solid battery.
The application of the composite electrode is characterized in that the semi-solid battery comprises a battery core assembled by a positive plate, an electrolyte membrane and a negative plate, and at least one of the positive plate and the negative plate is the composite electrode.
Has the advantages that: firstly, carbon coating is carried out on an inorganic solid electrolyte, so that the prepared carbon-coated inorganic solid electrolyte composite material has ionic conductivity and electronic conductivity, and then the carbon-coated inorganic solid electrolyte composite material is mixed with an electrode active material to prepare a composite electrode; the composite electrode is used for preparing the semi-solid battery, so that the safety performance of the battery can be improved, and the multiplying power and the cycle performance of the battery can be effectively improved.
Drawings
Fig. 1 is a flow chart of a method for manufacturing a composite electrode according to the present invention.
Detailed Description
The invention provides a composite electrode and a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to fig. 1, fig. 1 is a flowchart illustrating a method for manufacturing a composite electrode according to the present invention, which includes the steps of:
s10, carrying out carbon coating treatment on the inorganic solid electrolyte to obtain a carbon-coated inorganic solid electrolyte composite material;
s20, mixing the carbon-coated inorganic solid electrolyte composite material with an electrode active material and a conductive agent to obtain a premix;
s30, adding a binder and an organic solvent into the premix and mixing to obtain slurry;
and S40, coating the slurry on a metal foil, drying, and then carrying out cold pressing and sheet making treatment to obtain the composite electrode.
The invention firstly carries out carbon coating treatment on the inorganic solid electrolyte to ensure that the prepared carbon-coated inorganic solid electrolyte composite material has two performances of ionic conductivity and electronic conductivity, and then mixes the carbon-coated inorganic solid electrolyte composite material with an electrode active material to prepare the composite electrode. That is, compared with the method of directly adding solid electrolyte, the method of the invention for carbon coating the inorganic solid electrolyte can effectively improve the electronic conductivity of the inorganic solid electrolyte, has small impedance and good thermal stability, so that the composite electrode can be used for preparing the semi-solid battery, can improve the safety performance of the battery, and can also effectively improve the multiplying power and the cycle performance of the battery.
In some embodiments, the carbon-coated inorganic solid-state electrolyte composite is one or more of a carbon-coated NASICON-structured composite, a carbon-coated perovskite-structured composite, a carbon-coated anti-perovskite-structured composite, a carbon-coated LISICON-structured composite, and a carbon-coated garnet-structured composite. Wherein the carbon-coated NASICON structure material comprises Li 1+a Al a Ge 2-a (PO 4 ) 30 /C composite material or isomorphous heteroatom doped compound thereof, and Li 1+b Al b Ti 2-b (PO 4 ) 3 The material is one or more of a/C composite material or an isoatomic doped compound in the same crystal form, wherein a is more than or equal to 0 and less than or equal to 0.75, and b is more than or equal to 0 and less than or equal to 0.5; and/or the carbon-coated perovskite structure composite material comprises Li 3c La 2/3-c TiO 3 /C composite material or isomorphous heteroatom doped compound thereof, and Li 3/8 Sr 7/16 Ta 3/4 Hf 1/4 O 3 /C composite material or isomorphous heteroatom doped compound thereof, and Li 2d- e Sr 1-d Ta e Zr 1-e O 3 the/C composite material or one or more of isomorphous heteroatom doped compounds thereof, wherein C is more than or equal to 0.06 and less than or equal to 0.14, e is more than or equal to 0 and less than or equal to 0.75, and d is more than or equal to 0.75 e; and/or the carbon-coated anti-perovskite structure composite material comprises Li 3- 2z M z Ha l O/C composite material and Li 3 Any one or more of OC/C composite material or isomorphous heteroatom doped compound thereof, wherein z is more than or equal to 0 and less than or equal to 0.01, and the content of the C/C composite material is lower than or equal to 0M comprises Mg 2+ 、Ca 2+ 、Sr 2+ Or Ba 2+ One or more of cations, the Ha l Is element Cl or I; and/or the carbon-coated LISICON structural composite material comprises Li 4-f Si 1-f P f O 4 /C composite material or isomorphous heteroatom doped compound thereof, and Li 14 ZnGe 4 O 16 the/C composite material or one or more of isomorphous heteroatom doped compounds thereof, wherein f is more than or equal to 0.5 and less than or equal to 0.6; and/or the carbon-coated garnet structure composite material comprises Li 7-g La 3 Zr 2-g O 12 the/C composite material or the isomorphous heteroatom doped compound thereof has the g being more than or equal to 0 and less than or equal to 1.
In some embodiments, the particle size D50 of the inorganic solid electrolyte in the carbon-coated inorganic solid electrolyte composite material is 0.1 to 100 μm, and may be, for example, 0.5 μm, 5 μm, 15 μm, 20 μm, 25 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, or 95 μm, or the like. In this embodiment, if the particle size of the inorganic solid electrolyte is too small, the coating effect of the material has great technical difficulty, and the electronic conductivity of the inorganic material cannot be obviously improved; if the particle size of the inorganic solid electrolyte is too large, the interface resistance increases, and ion transport is blocked. Preferably, the particle size of the oxide solid electrolyte is 0.2 to 20 μm.
In some embodiments, when the composite electrode is a positive electrode, then the electrode active material is a positive electrode active material, which is LiCoO 2 、LiNiO 2 、LiMnO 2 、LiNi 0.5 Mn 1.5 O 4 、LiNi x Co 1-x O 2 、LiNi x Co y Mn 1-x-y O 2 And LiNi x Co y Al 1-x-y O 2 Wherein, 0<x<1，0<y<1，0<x+y<1. When the composite electrode is a negative electrode, the electrode active material is a negative active material, and the negative active material is hard carbon, graphite, silicon carbon, SiO x And Li 4 Ti 5 O 12 One or more of (a).
In some embodiments, the carbon-coated inorganic solid electrolyte composite material comprises 0.1-50% of the total mass of the electrode active material and the carbon-coated inorganic solid electrolyte composite material, for example, 0.5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, etc. In this embodiment, if the content of the carbon-coated inorganic solid electrolyte composite material is too large, the content of the electrode active material is relatively reduced, and at the same time, ion transport is hindered, and the energy density is reduced; if the content of the carbon-coated inorganic solid electrolyte composite material is too low, the safety performance of the composite electrode is poor, and the safety performance of the battery cannot be obviously improved. Preferably, the carbon-coated inorganic solid electrolyte composite material accounts for 1-10% of the total mass of the electrode active material and the carbon-coated inorganic solid electrolyte composite material.
In some embodiments, the conductive agent is one or more of SP, KS-6, CNT, graphene, but is not limited thereto. The adhesive is one or more of PVDFHSV900 and PVDFsolef5130, but is not limited to the above. The organic solvent is NMP, but is not limited thereto.
In some embodiments, a composite electrode is also provided, which is prepared by the method for preparing the composite electrode.
In some embodiments, there is also provided a use of a composite electrode, wherein the composite electrode of the present invention is used to prepare a semi-solid battery. In this embodiment, the semi-solid battery includes a battery cell assembled by a positive plate, an electrolyte membrane, and a negative plate, and at least one of the positive plate and the negative plate is a composite electrode.
The invention is further illustrated by the following specific examples:
example 1
1. A positive electrode active material Ni88(Li [ Ni ] 0.88 Co 0.02 Mn 0.1 ]O 2 ) LATP oxide (particle diameter 1 μm, Li) 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 ) Feeding the materials and SP according to the mass ratio of 94:3:1.5, and premixing for 1h in advance under the condition of the rotating speed of 500 rpm; premixingAdding PVDF and NMP into the materials to be stirred at 2500rpm to prepare anode slurry;
2. uniformly coating the positive electrode slurry on an aluminum foil, drying, and then carrying out cold pressing and sheet making to obtain a positive electrode sheet;
3. coating a layer of oxidation-polymer electrolyte membrane on the composite positive plate;
4. laminating, assembling and baking the composite anode piece coated with the composite electrolyte membrane and the silicon-carbon cathode (active material: binder: conductive agent: 97.8:1.7: 0.5);
5. and injecting an electrolyte into the baked battery core for packaging, soaking for 24 hours to enable the electrolyte to fully soak the pole piece, and then heating and curing the obtained battery at 60 ℃ for 6 hours to obtain the semi-solid battery containing the inorganic solid positive pole piece.
Example 2
1. A positive electrode active material Ni88(Li [ Ni ] 0.88 Co 0.02 Mn 0.1 ]O 2 ) LATP/C composite material (particle diameter 1 μm, Li) 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 ) Feeding the materials and SP according to the mass ratio of 96:1:1.5, and premixing for 1h in advance under the condition of the rotating speed of 500 rpm; adding PVDF and NMP into the premixed material, and stirring at 2500rpm to prepare anode slurry;
2. uniformly coating the positive electrode slurry on an aluminum foil, drying, and then carrying out cold pressing and sheet making to obtain a positive electrode sheet;
3. coating a layer of oxidation-polymer electrolyte membrane on the composite positive plate;
4. laminating, assembling and baking the composite anode piece coated with the composite electrolyte membrane and the silicon-carbon cathode (active material: binder: conductive agent: 97.8:1.7: 0.5);
5. and injecting an electrolyte into the baked battery core for packaging, soaking for 24 hours to enable the electrolyte to fully soak the pole piece, and then heating and curing the obtained battery at 60 ℃ for 6 hours to obtain the semi-solid battery containing the carbon-coated inorganic solid positive pole piece.
Example 3
1. A positive electrode active material Ni88(Li [ Ni ]) 0.88 Co 0.02 Mn 0.1 ]O 2 ) LATP/C composite material (particle diameter 1 μm, Li) 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 ) Feeding the materials and SP according to the mass ratio of 94:3:1.5, and premixing for 1h in advance under the condition of the rotating speed of 500 rpm; adding PVDF and NMP into the premixed material, and stirring at 2500rpm to prepare anode slurry;
2. uniformly coating the positive electrode slurry on an aluminum foil, drying, and then carrying out cold pressing and sheet making to obtain a positive electrode sheet;
3. coating a layer of oxidation-polymer electrolyte membrane on the composite positive plate;
4. laminating, assembling and baking the composite anode piece coated with the composite electrolyte membrane and the silicon-carbon cathode (active material: binder: conductive agent: 97.8:1.7: 0.5);
5. and injecting an electrolyte into the baked battery core for packaging, soaking for 24 hours to enable the electrolyte to fully soak the pole piece, and then heating and curing the obtained battery at 60 ℃ for 6 hours to obtain the semi-solid battery containing the carbon-coated inorganic solid positive pole piece.
Example 4
1. A positive electrode active material Ni88(Li [ Ni ] 0.88 Co 0.02 Mn 0.1 ]O 2 ) LATP/C composite material (particle diameter 1 μm, Li) 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 ) Feeding the materials and SP according to the mass ratio of 92:5:1.5, and premixing for 1h in advance under the condition of the rotating speed of 500 rpm; adding PVDF and NMP into the premixed material, and stirring at 2500rpm to prepare anode slurry;
2. uniformly coating the positive electrode slurry on an aluminum foil, drying, and then performing cold pressing and sheet making to obtain a positive electrode sheet;
3. coating a layer of oxidation-polymer electrolyte membrane on the composite positive plate;
4. laminating, assembling and baking the composite anode piece coated with the composite electrolyte membrane and the silicon-carbon cathode (active material: binder: conductive agent: 97.8:1.7: 0.5);
5. and injecting an electrolyte into the baked battery core for packaging, soaking for 24 hours to enable the electrolyte to fully soak the pole piece, and then heating and curing the obtained battery at 60 ℃ for 6 hours to obtain the semi-solid battery containing the carbon-coated inorganic solid positive pole piece.
Example 5
1. A positive electrode active material Ni88(Li [ Ni ] 0.88 Co 0.02 Mn 0.1 ]O 2 ) LATP/C composite material (particle diameter 1 μm, Li) 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 ) Feeding the materials and SP according to the mass ratio of 90:7:1.5, and premixing for 1h in advance under the condition of the rotating speed of 500 rpm; adding PVDF and NMP into the premixed material, and stirring at 2500rpm to prepare anode slurry;
2. uniformly coating the positive electrode slurry on an aluminum foil, drying, and then performing cold pressing and sheet making to obtain a positive electrode sheet;
3. coating a layer of oxidation-polymer electrolyte membrane on the composite positive plate;
4. laminating, assembling and baking the composite anode piece coated with the composite electrolyte membrane and the silicon-carbon cathode (active material: binder: conductive agent: 97.8:1.7: 0.5);
5. and injecting an electrolyte into the baked battery core for packaging, soaking for 24 hours to enable the electrolyte to fully soak the pole piece, and then heating and curing the obtained battery at 60 ℃ for 6 hours to obtain the semi-solid battery containing the carbon-coated inorganic solid positive pole piece.
Example 6
1. A positive electrode active material Ni88(Li [ Ni ] 0.88 Co 0.02 Mn 0.1 ]O 2 ) LATP/C composite material (particle diameter 1 μm, Li) 1.2 Al 0.2 Ti 1.8 (PO 4 ) 3 ) Feeding the materials and SP according to the mass ratio of 87:10:1.5, and premixing for 1h in advance under the condition of the rotating speed of 500 rpm; adding PVDF and NMP into the premixed material, and stirring at 2500rpm to prepare anode slurry;
2. uniformly coating the positive electrode slurry on an aluminum foil, drying, and then carrying out cold pressing and sheet making to obtain a positive electrode sheet;
3. coating a layer of oxidation-polymer electrolyte membrane on the composite anode sheet;
4. laminating, assembling and baking the composite anode piece coated with the composite electrolyte membrane and the silicon-carbon cathode (active material: binder: conductive agent: 97.8:1.7: 0.5);
5. and injecting an electrolyte into the baked battery core for packaging, soaking for 24 hours to enable the electrolyte to fully soak the pole piece, and then heating and curing the obtained battery at 60 ℃ for 6 hours to obtain the semi-solid battery containing the carbon-coated inorganic solid positive pole piece.
Example 7
1. Mixing a negative electrode active material Si-C (450), LLZO oxide (particle diameter 1 μm, Li) 7 La 3 Zr 2 O 12 ) Feeding the materials and SP according to the mass ratio of 93.5:3:1.0, and premixing for 1h in advance under the condition of the rotating speed of 500 rpm; adding the glue solution into the premixed material, stirring at 2000rpm for 4h, and stirring to prepare cathode slurry;
2. uniformly coating the negative electrode slurry on a copper foil, drying, and then carrying out cold pressing and sheet making to obtain a negative electrode sheet;
3. coating an oxidation-polymer electrolyte layer on the composite negative plate;
4. laminating, assembling and baking the composite negative pole piece coated with the composite electrolyte layer and the NCM811 positive pole (active material: binder: conductive agent: 97.0:1.5: 1.5);
5. and injecting electrolyte into the baked battery core for packaging, soaking for 24h to enable the electrolyte to fully soak the pole piece, and then heating and curing the obtained battery at 60 ℃ for 6h to obtain the semi-solid battery containing the inorganic solid negative pole piece.
Example 8
1. Mixing the negative active material Si-C (450), LLZO/C oxide (particle diameter 1 μm, Li) 7 La 3 Zr 2 O 12 ) Feeding the materials and SP according to the mass ratio of 95.5:1:1.0, and premixing for 1h in advance under the condition of the rotating speed of 500 rpm; adding the glue solution into the premixed material, stirring at 2000rpm for 4h, and stirring to prepare cathode slurry;
2. uniformly coating the negative electrode slurry on a copper foil, drying, and then carrying out cold pressing and sheet making to obtain a negative electrode sheet;
3. coating an oxidation-polymer electrolyte layer on the composite negative plate;
4. laminating, assembling and baking the composite negative pole piece coated with the composite electrolyte membrane and the NCM811 positive pole (active material: binder: conductive agent: 97.0:1.5: 1.5);
5. and injecting electrolyte into the baked battery core for packaging, soaking for 24h to enable the electrolyte to fully soak the pole piece, and then heating and curing the obtained battery at 60 ℃ for 6h to obtain the semi-solid battery containing the inorganic solid negative pole piece.
Example 9
1. Mixing the negative active material Si-C (450), LLZO/C oxide (particle diameter 1 μm, Li) 7 La 3 Zr 2 O 12 ) Feeding the materials and SP according to the mass ratio of 93.5:3:1.0, and premixing for 1h in advance under the condition of the rotating speed of 500 rpm; adding the glue solution into the premixed material, stirring at 2000rpm for 4h, and stirring to prepare cathode slurry;
2. uniformly coating the negative electrode slurry on a copper foil, drying, and then carrying out cold pressing and sheet making to obtain a negative electrode sheet;
3. coating an oxidation-polymer electrolyte layer on the composite negative plate;
4. laminating, assembling and baking the composite negative pole piece coated with the composite electrolyte layer and the NCM811 positive pole (active material: binder: conductive agent: 97.0:1.5: 1.5);
5. and injecting electrolyte into the baked battery core for packaging, soaking for 24h to enable the electrolyte to fully soak the pole piece, and then heating and curing the obtained battery at 60 ℃ for 6h to obtain the semi-solid battery containing the inorganic solid negative pole piece.
Example 10
1. Mixing the negative active material Si-C (450), LLZO/C oxide (particle diameter 1 μm, Li) 7 La 3 Zr 2 O 12 ) Feeding the materials and SP according to the mass ratio of 91.5:5:1.0, and premixing for 1h in advance under the condition of the rotating speed of 500 rpm; adding the glue solution into the premixed material, stirring at 2000rpm for 4h, and stirring to prepare cathode slurry;
2. uniformly coating the negative electrode slurry on a copper foil, drying, and then carrying out cold pressing and sheet making to obtain a negative electrode sheet;
3. coating a layer of oxidation-polymer electrolyte membrane on the composite negative plate;
4. laminating, assembling and baking the composite negative pole piece coated with the composite electrolyte membrane and the NCM811 positive pole (active material: binder: conductive agent: 97.0:1.5: 1.5);
5. and injecting electrolyte into the baked battery core for packaging, soaking for 24h to enable the electrolyte to fully soak the pole piece, and then heating and curing the obtained battery at 60 ℃ for 6h to obtain the semi-solid battery containing the inorganic solid negative pole piece.
Example 11
1. Mixing the negative active material Si-C (450), LLZO/C oxide (particle diameter 1 μm, Li) 7 La 3 Zr 2 O 12 ) Feeding the materials and SP according to the mass ratio of 89.5:7:1.0, and premixing for 1h in advance under the condition of the rotating speed of 500 rpm; adding the glue solution into the premixed material, stirring at 2000rpm for 4h, and stirring to prepare cathode slurry;
2. uniformly coating the negative electrode slurry on a copper foil, drying, and then carrying out cold pressing and sheet making to obtain a negative electrode sheet;
3. coating a layer of oxidation-polymer electrolyte membrane on the composite negative plate;
4. laminating, assembling and baking the composite negative pole piece coated with the composite electrolyte membrane and the NCM811 positive pole (active material: binder: conductive agent: 97.0:1.5: 1.5);
5. and injecting electrolyte into the baked battery core for packaging, soaking for 24h to enable the electrolyte to fully soak the pole piece, and then heating and curing the obtained battery at 60 ℃ for 6h to obtain the semi-solid battery containing the inorganic solid negative pole piece.
Example 12
1. Mixing the negative active material Si-C (450), LLZO/C oxide (particle diameter 1 μm, Li) 7 La 3 Zr 2 O 12 ) Feeding the materials and SP according to the mass ratio of 87.5:10:1.0, and premixing for 1h in advance under the condition of the rotating speed of 500 rpm; adding the glue solution into the premixed material, stirring at 2000rpm for 4h, and stirring to prepare cathode slurry;
2. uniformly coating the negative electrode slurry on a copper foil, drying, and then carrying out cold pressing and sheet making to obtain a negative electrode sheet;
3. coating a layer of oxidation-polymer electrolyte membrane on the composite negative plate;
4. laminating, assembling and baking the composite negative pole piece coated with the composite electrolyte membrane and the NCM811 positive pole (active material: binder: conductive agent: 97.0:1.5: 1.5);
5. and injecting electrolyte into the baked battery core for packaging, soaking for 24h to enable the electrolyte to fully soak the pole piece, and then heating and curing the obtained battery at 60 ℃ for 6h to obtain the semi-solid battery containing the inorganic solid negative pole piece.
The semi-solid batteries prepared in examples 1 to 12 were subjected to performance tests, and the results are shown in table 1.
Table 1 semi-solid state battery performance test results
Figure BDA0003599279390000121
Figure BDA0003599279390000131
Figure BDA0003599279390000141
From the results in table 1, it can be seen that the carbon-coated inorganic electrolyte composite material is blended in the positive electrode or the negative electrode of the semi-solid battery, so that the electronic conductivity of the electrode can be effectively improved, the safety performance of the battery can be improved, and the performances of the battery, such as multiplying power, cycle and the like, can be improved.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.

Claims (9)

1. A method for preparing a composite electrode, comprising the steps of:
carrying out carbon coating treatment on the inorganic solid electrolyte to prepare a carbon-coated inorganic solid electrolyte composite material;
mixing the carbon-coated inorganic solid electrolyte composite material with an electrode active material and a conductive agent to obtain a premix;
adding a binder and an organic solvent into the premix and mixing to obtain slurry;
and coating the slurry on a metal foil, drying, and then carrying out cold pressing and flaking treatment to obtain the composite electrode.
2. The method for producing a composite electrode according to claim 1, wherein the carbon-coated inorganic solid electrolyte composite material is one or more of a carbon-coated NASICON-structured composite material, a carbon-coated perovskite-structured composite material, a carbon-coated anti-perovskite-structured composite material, a carbon-coated LISICON-structured composite material, and a carbon-coated garnet-structured composite material.
3. The method of claim 2, wherein the carbon-coated NASICON structural material comprises Li 1+a Al a Ge 2-a (PO 4 ) 30 /C composite material or isomorphous heteroatom doped compound thereof, and Li 1+b Al b Ti 2-b (PO 4 ) 3 The material is one or more of a/C composite material or an isoatomic doped compound in the same crystal form, wherein a is more than or equal to 0 and less than or equal to 0.75, and b is more than or equal to 0 and less than or equal to 0.5; and/or the carbon-coated perovskite structure composite material comprises Li 3c La 2/3-c TiO 3 /C composite material or isomorphous heteroatom doped compound thereof, and Li 3/8 Sr 7/16 Ta 3/4 Hf 1/4 O 3 /C composite material or isomorphous heteroatom doped compound thereof, and Li 2d-e Sr 1- d Ta e Zr 1-e O 3 The material is one or more of an/C composite material or an isomorphous heteroatom doped compound thereof, wherein C is more than or equal to 0.06 and less than or equal to 0.14, e is more than or equal to 0 and less than or equal to 0.75, and d is 0.75 e; and/or the carbon-coated anti-perovskite structure composite material comprises Li 3- 2z M z Ha l O/C composite material and Li 3 Any one or more of OC/C composite material or isomorphous heteroatom doped compound thereof, wherein z is more than or equal to 0 and less than or equal to 0.01, and M comprises Mg 2+ 、Ca 2+ 、Sr 2+ Or Ba 2+ One or more of cations, the Ha l Is element Cl or I; and/or the carbon-coated LISICON structural composite material comprises Li 4-f Si 1-f P f O 4 /C composite material or isomorphous heteroatom doped compound thereof, and Li 14 ZnGe 4 O 16 the/C composite material or one or more of isomorphous heteroatom doped compounds thereof, wherein f is more than or equal to 0.5 and less than or equal to 0.6; and/or the carbon-coated garnet structure composite material comprises Li 7-g La 3 Zr 2-g O 12 the/C composite material or the isomorphous heteroatom doped compound thereof has the g being more than or equal to 0 and less than or equal to 1.
4. The method for producing a composite electrode according to claim 1, wherein the particle diameter D50 of the inorganic solid electrolyte in the carbon-coated inorganic solid electrolyte composite material is 0.1 to 100 μm.
5. The method of manufacturing a composite electrode according to claim 1, wherein the electrode active material is a positive electrode active material or a negative electrode active material, and the positive electrode active material is LiCoO 2 、LiNiO 2 、LiMnO 2 、LiNi 0.5 Mn 1.5 O 4 、LiNi x Co 1-x O 2 、LiNi x Co y Mn 1-x-y O 2 And LiNi x Co y Al 1-x-y O 2 Wherein, 0<x<1，0<y<1，0<x+y<1; the negative active material is hard carbon, graphite, silicon carbon, SiOx and Li 4 Ti 5 O 12 One or more of (a).
6. The method of producing a composite electrode according to claim 1, wherein the carbon-coated inorganic solid electrolyte composite material accounts for 0.1 to 50% of the total mass of the electrode active material and the carbon-coated inorganic solid electrolyte composite material.
7. A composite electrode produced by the method for producing a composite electrode according to any one of claims 1 to 6.
8. Use of a composite electrode according to claim 7 for the preparation of a semi-solid battery.
9. The use of the composite electrode according to claim 8, wherein the semi-solid battery comprises a cell assembled by a positive plate, an electrolyte membrane and a negative plate, and at least one of the positive plate and the negative plate is the composite electrode.
CN202210396657.9A 2022-04-15 2022-04-15 Composite electrode and preparation method and application thereof Pending CN114864872A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210396657.9A CN114864872A (en) 2022-04-15 2022-04-15 Composite electrode and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210396657.9A CN114864872A (en) 2022-04-15 2022-04-15 Composite electrode and preparation method and application thereof

Publications (1)

Publication Number Publication Date
CN114864872A true CN114864872A (en) 2022-08-05

Family

ID=82631874

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210396657.9A Pending CN114864872A (en) 2022-04-15 2022-04-15 Composite electrode and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN114864872A (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110098432A (en) * 2019-06-03 2019-08-06 哈尔滨工业大学 A kind of preparation method and applications of carbon fiber cladding solid electrolyte material
CN111403806A (en) * 2020-04-17 2020-07-10 中国科学院物理研究所 Carbon-coated solid electrolyte material and preparation method and application thereof
CN113258032A (en) * 2021-04-19 2021-08-13 浙江锋锂新能源科技有限公司 Negative electrode material, negative electrode slurry, battery cell, low-temperature-resistant battery and preparation method thereof
CN113363436A (en) * 2021-05-14 2021-09-07 宁波梅山保税港区锂泰企业管理合伙企业(有限合伙) Lithium ion battery with high energy density and high cycle performance
CN113488693A (en) * 2021-07-01 2021-10-08 重庆锦添翼新能源科技有限公司 Double-layer graphene-coated solid electrolyte composite material and preparation method thereof
CN113745638A (en) * 2020-05-27 2021-12-03 北京卫蓝新能源科技有限公司 High-safety and high-power ternary positive plate for lithium battery and preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110098432A (en) * 2019-06-03 2019-08-06 哈尔滨工业大学 A kind of preparation method and applications of carbon fiber cladding solid electrolyte material
CN111403806A (en) * 2020-04-17 2020-07-10 中国科学院物理研究所 Carbon-coated solid electrolyte material and preparation method and application thereof
CN113745638A (en) * 2020-05-27 2021-12-03 北京卫蓝新能源科技有限公司 High-safety and high-power ternary positive plate for lithium battery and preparation method and application thereof
CN113258032A (en) * 2021-04-19 2021-08-13 浙江锋锂新能源科技有限公司 Negative electrode material, negative electrode slurry, battery cell, low-temperature-resistant battery and preparation method thereof
CN113363436A (en) * 2021-05-14 2021-09-07 宁波梅山保税港区锂泰企业管理合伙企业(有限合伙) Lithium ion battery with high energy density and high cycle performance
CN113488693A (en) * 2021-07-01 2021-10-08 重庆锦添翼新能源科技有限公司 Double-layer graphene-coated solid electrolyte composite material and preparation method thereof

Similar Documents

Publication Publication Date Title
CN108565412B (en) Carbon fluoride mixed positive pole piece and preparation method thereof
CN110707287B (en) Metal lithium negative electrode, preparation method thereof and lithium battery
EP2631972A1 (en) Method for producing composition for forming positive electrode material mixture layer and method for producing lithium ion secondary battery
Xue et al. Effect of particle size on rate capability and cyclic stability of LiNi 0.5 Mn 1.5 O 4 cathode for high-voltage lithium ion battery
KR20140101640A (en) Negative electrode active material for rechargeable lithium battery, and method for preparing the same
CN113937289A (en) Dry-process battery pole piece based on graphene, battery and manufacturing method of dry-process battery pole piece
CN110268557A (en) Use the prelithiation of lithium metal and inorganic composite layers
CN105226256A (en) For modified cathode material and the lithium titanate battery of lithium titanate battery
CN110098387B (en) Lithium phosphate and conductive carbon material coated ternary cathode material and preparation method and application thereof
JPWO2019216275A1 (en) Positive electrode composition for lithium ion secondary battery, positive electrode for lithium ion secondary battery, and lithium ion secondary battery
JP2012033364A (en) Method for manufacturing electrode of lithium ion secondary battery, and method for manufacturing lithium ion secondary battery
TW200304243A (en) Cathode compositions, cathodes, methods of producing cathodes and lithium secondary batteries including the same
US9466828B2 (en) Method for preparing electrode active material for rechargeable lithium battery, electrode active material for rechargeable lithium battery, and rechargeable lithium battery
CN104157466A (en) Super lithium-ion capacitor and manufacturing method thereof
Zarei-Jelyani et al. Unraveling the role of binder concentration on the electrochemical behavior of mesocarbon microbead anode in lithium–ion batteries: understanding the formation of the solid electrolyte interphase
CN113903981A (en) Lithium ion battery and preparation method and application thereof
CN101826640A (en) Pole core for lithium ion battery and lithium ion battery using pole core
CN105870454A (en) Application method of graphene as conductive agent to positive electrode slurry of lithium ion battery
JP6725261B2 (en) Lithium ion secondary battery
CN112490495A (en) Inorganic-organic composite solid electrolyte, preparation method and solid lithium battery
CN111009692A (en) Manufacturing method of lithium ion battery and lithium ion battery
CN103258989A (en) Electrode for lithium secondary battery, manufacturing method thereof and lithium secondary battery
KR101122938B1 (en) Preparation method of electrode active material particle
CN108461711A (en) A kind of nickel-cobalt-manganese ternary anode composite of room temperature solid flexible battery and preparation method thereof and application
CN114864872A (en) Composite electrode and preparation method and application thereof

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