CN114583110B - Negative electrode plate, preparation method thereof and application thereof in solid-state battery - Google Patents

Negative electrode plate, preparation method thereof and application thereof in solid-state battery Download PDF

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CN114583110B
CN114583110B CN202210261361.6A CN202210261361A CN114583110B CN 114583110 B CN114583110 B CN 114583110B CN 202210261361 A CN202210261361 A CN 202210261361A CN 114583110 B CN114583110 B CN 114583110B
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negative electrode
carbonate
electrode plate
ester solution
vinylene carbonate
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CN114583110A (en
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李峥
冯玉川
何泓材
杨帆
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Suzhou Qingtao New Energy S&T Co Ltd
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Suzhou Qingtao New Energy S&T Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • 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
    • 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
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M2004/027—Negative 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a negative electrode plate, a preparation method thereof and application thereof in a solid-state battery. The method comprises the following steps: immersing the negative electrode plate into an ester solution to obtain the negative electrode plate containing the carbonate organic layer, wherein the ester solution comprises vinylene carbonate, and the negative electrode plate comprises metallic lithium. Aiming at the problems that in the prior art, carbonate materials react with metal lithium under electrochemical induction to form loss, so that the surface of the metal lithium still has a certain degree of deposition phenomenon. The film forming additive is an unsaturated carbide additive (vinylene carbonate), and the vinylene carbonate has lower reduction potential than a carbonic ester solvent, so that the vinylene carbonate is easier to reduce, and a small amount of vinylene carbonate is added into the carbonic ester solvent to protect a carbonic ester protective layer better and is reduced in preference to the carbonic ester protective layer to form a complete carbonic ester protective layer.

Description

Negative electrode plate, preparation method thereof and application thereof in solid-state battery
The application is the application number: 202010129564.0, filing date: 28 days of 2 months in 2020, name: a negative electrode sheet, a method of making the same and applications in solid state batteries are disclosed.
Technical Field
The invention belongs to the technical field of solid-state batteries, and particularly relates to a negative electrode plate, a preparation method thereof and application thereof in a solid-state battery.
Background
The requirements of the electric automobile and the power grid on the energy storage system are continuously improved, so that the requirement of a high-capacity battery is increasingly urgent, and the metal lithium has about ten times higher theoretical capacity than graphite, and has very wide application prospect, but since the first report of the lithium metal cathode in the 70 th century, the application of the metal lithium is greatly limited by the problems of more surface side reactions, unstable SEI film and the like, so that the metal lithium cathode is not applied industrially all the time. In recent years, solid electrolytes are considered as effective means for effectively solving the problem of application of metallic lithium because they are nonflammable, non-corrosive, non-volatile, and free from the problem of leakage.
However, there are a number of practical problems with solid-state electrolytes, such as the deposition of metallic lithium on the surface of the metallic lithium when applied to an all-solid system, which can adversely affect the overall performance of the battery. Therefore, how to protect a metallic lithium anode is also a technical problem to be solved by a solid electrolyte battery.
At present, the addition of a protective layer on the surface of lithium metal is a conventional method for protecting a metal lithium negative electrode, and researches prove that the application of a carbonate protective layer on the surface of the metal lithium negative electrode has beneficial effects on improving the overall performances such as the first efficiency of a battery; the applicant has found in previous studies that in solid state batteries, even carbonate materials in the form of a protective layer react with metallic lithium under electrochemical induction to form losses by the following mechanism:
therefore, the protective layer is slowly worn out with the lapse of the use time, so that the capacity retention rate of the battery is lowered; meanwhile, the decomposition reaction of the protective layer is accompanied by a large amount of irreversible gas generation, which also adversely affects the overall performance of the battery. Therefore, how to ensure the integrity of the carbonate protective film is a technical problem to be solved.
CN108417774a discloses a process for mixing negative electrode slurry with pre-lithiation effect and lithium battery, under the environmental condition of dew point-40 to-50 deg.c, stirring the negative electrode active material and conductive agent, adding conductive slurry, adding NMP twice, kneading and mixing, finally adding metal lithium sheet and electrolyte containing film-forming additive, dispersing and pre-lithiating. However, the method cannot only solve the problem of electrochemical consumption of carbonate solvents in the electrolyte environment, and does not relate to how to effectively solve the problem of deposition on the surface of lithium metal.
Therefore, how to protect the integrity of the carbonate protective film in the lithium metal negative electrode is a technical problem that needs to be solved in the current solid electrolyte battery.
Disclosure of Invention
Aiming at the problems that in the prior art, carbonate materials react with metal lithium under electrochemical induction to form loss, so that when the metal lithium is applied to an all-solid-state system, the surface of the metal lithium still has a certain deposition phenomenon. The invention aims to provide a negative electrode plate, a preparation method thereof and application thereof in a solid-state battery. According to the invention, a small amount of vinylene carbonate is added into the ester solvent, so that a better protection effect can be achieved on the carbonate protective layer.
To achieve the purpose, the invention adopts the following technical scheme:
the invention aims at providing a preparation method of a negative electrode plate, which comprises the following steps: immersing the negative electrode plate into an ester solution to obtain the negative electrode plate containing the carbonate organic layer, wherein the ester solution comprises vinylene carbonate, and the negative electrode plate comprises metallic lithium.
The film forming additive is an unsaturated carbide additive (vinylene carbonate), and the vinylene carbonate has lower reduction potential than a carbonic ester solvent, so that the vinylene carbonate is easier to reduce, and a small amount of vinylene carbonate is added into the carbonic ester solvent to protect a carbonic ester protective layer better and is reduced in preference to the carbonic ester protective layer to form a complete SEI film.
Preferably, the negative electrode sheet is a metallic lithium sheet or a metallic lithium sheet coated with a graphite layer, preferably a metallic lithium sheet coated with a graphite layer.
VC (vinylene carbonate) can reduce the high active point activity of the graphite surface, forming a surface film of polymer structure.
Preferably, in the metallic lithium sheet coated with a graphite layer, the thickness of the graphite layer is 5 to 100 μm, for example, 10 μm, 20 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 95 μm, or the like.
Preferably, in the metallic lithium sheet coated with a graphite layer, the surface roughness of the graphite layer is 3 to 15 μm, for example, 3 μm, 4 μm, 5 μm, 8 μm, 10 μm, 12 μm, 14 μm, or the like.
The proper roughness helps to improve the adhesion between the film layers, and on the other hand, too much roughness will have to increase the thickness of the graphite layer, resulting in reduced performance of the electrode sheet.
The applicant proves that after the graphite layer is added, the integrity of the protective layer is beneficial, the interaction between VC and graphite enables the film layer formed between the protective layer and the electrode layer to be more complete, and meanwhile, the bonding force between the protective layer and the graphite layer can be further improved through effective treatment of the surface roughness of the graphite layer.
Preferably, in the metallic lithium sheet coated with a graphite layer, the particle size of graphite is less than 400 mesh.
Preferably, the concentration of the solute in the ester solution is 0.5 to 10mol/L, for example, 1mol/L, 2mol/L, 3mol/L, 4mol/L, 5mol/L, 6mol/L, 7mol/L, 8mol/L, 9mol/L, or the like.
Preferably, the concentration of vinylene carbonate in the ester solution is 0.1-2 mol/L, for example 0.2mol/L, 0.5mol/L, 0.6mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.5mol/L, 1.6mol/L or 1.8mol/L, etc.
The concentration of vinylene carbonate in the selected ester solution is too high, so that the structural integrity of the protective layer is affected; if the concentration is too small, the protective layer cannot be effectively protected.
Preferably, the solute in the ester solution comprises LiNO 3 、KNO 3 、NaNO 3 、LiPF 2 、LiPF 6 、LiClO 4 、KClO 4 、KPF 6 、LiBF 4 、LiClO 4 、LiBOB、LiDFOB、LiAsF 6 、LiSbF 6 、LiCF 3 SO 3 、LiN(SO 2 CF 3 ) 2 、LiN(SO 2 C 2 F 5 ) 2 、LiN(SO 2 CF 3 ) 2 、LiN(SO 2 CF 3 ) 3 、LiB(CF 3 ) 4 Or LiBF 3 (C 2 F 5 ) Any one of the followingOr a combination of at least two, preferably LiNO 3 、LiPF 6 、LiBOB、LiCF 3 SO 3 、LiN(SO 2 CF 3 ) 2 And LiBF 3 (C 2 F 5 ) Any one or a combination of at least two of these.
Preferably, the solvent in the ester solution comprises any one or a combination of at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, ethylmethyl carbonate and diethyl carbonate.
Preferably, the negative electrode sheet is immersed in the ester solution for 1-48 hours, for example, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 25 hours, 28 hours, 30 hours, 32 hours, 35 hours, 38 hours, 40 hours or 45 hours, etc.
The soaking time is 1-48 h, and the longer the soaking time is, the thicker the thicknesses of the inorganic layer and the carbonate organic layer on the surface of the negative electrode are, so that the optimal time is 1-48 h for obtaining excellent electrochemical performance.
Preferably, the negative electrode plate is immersed in the ester solution and then dried, preferably in a glove box.
Preferably, the drying temperature is 60 to 80 ℃, for example 62 ℃, 64 ℃, 65 ℃, 66 ℃, 68 ℃, 70 ℃, 72 ℃, 74 ℃, 75 ℃, 76 ℃, 78 ℃, or the like.
The second object of the invention is to provide a negative electrode plate, which is prepared by the method according to one of the objects.
It is a further object of the present invention to provide a solid-state battery including the two negative electrode tabs.
The material compositions of the positive electrode material and the electrolyte in the solid-state battery are not particularly limited in the present invention, and may be selected by those skilled in the art according to actual conditions.
Compared with the prior art, the invention has the following beneficial effects:
aiming at the problem that the carbonate material which is used as the protective layer still has loss under electrochemical induction, VC is used as an additive to form a film on the surface of the negative electrode so as to achieve the effect of forming a complete carbonate protective layer on the surface of the negative electrode; meanwhile, according to the characteristic of VC, the special graphite layer is formed on the surface layer of the negative electrode, so that the protection effect of the protective layer is improved.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The ester solution described in this example: the solute is LiNO 3 And KNO 3 The mixed material is obtained by mixing according to the mass ratio of 1:1, the concentration of solute in the ester solution is 5mol/L, the solvent is dimethyl carbonate, and the concentration of vinylene carbonate is 1mol/L;
(1) Preparing a negative electrode plate: immersing the lithium sheet into an ester solution for 24 hours, and drying at 70 ℃ in a glove box to obtain a cathode sheet containing a carbonate organic layer;
(2) Preparing a positive electrode plate: positive electrode active material (lithium iron phosphate): conductive carbon black: mixing the binder PVDF=90:5:5 by mass, mixing slurry by using NMP as a solvent, coating the slurry on an aluminum foil, and carrying out vacuum drying at 90 ℃ to obtain a positive electrode plate;
(3) Preparation of all-solid-state electrolyte battery: and assembling the positive electrode plate, the negative electrode plate and the solid electrolyte (lithium lanthanum zirconium oxide) into a battery.
Example 2
The difference from example 1 is that a graphite layer having a surface roughness of 3 μm, a thickness of 20 μm and a particle diameter of 500 mesh of graphite was formed on the surface of the lithium sheet.
Example 3
The difference from example 1 is that a graphite layer having a surface roughness of 20 μm, a thickness of 40 μm and a particle diameter of 500 mesh of graphite was formed on the surface of the lithium sheet.
Example 4
The difference from example 1 is that a graphite layer having a surface roughness of 15 μm, a thickness of 20 μm and a particle diameter of 500 mesh of graphite was formed on the surface of the lithium sheet.
Example 5
The difference from example 1 is that a graphite layer having a surface roughness of 25 μm, a thickness of 100 μm and a particle diameter of 500 mesh of graphite was formed on the surface of the lithium sheet.
Comparative example 1
The difference from example 1 is that vinylene carbonate is not added.
Comparative example 2
The difference from example 1 is that vinylene carbonate is replaced by an equivalent amount of propylene sulfite.
Performance test:
the batteries obtained in each example and comparative example were subjected to charge and discharge tests at 25.+ -. 2 ℃ at a charge and discharge voltage of 2.75 to 4.25V and a current density of 0.1C, and the first efficiency, 10 cycles of capacity retention, 20 cycles of capacity retention and 30 cycles of capacity retention were respectively tested, and the test results are shown in Table 1:
TABLE 1
It is known from example 1, comparative example 1 and comparative example 2 that not all film forming additives are suitable for the solid state battery system according to the present invention, but propylene sulfite and ethylene carbonate are conventional film forming additives in the art, but propylene sulfite does not improve the overall performance of the battery, but rather the battery performance is greatly deteriorated.
Comparative examples 1 and 2 show that the addition of the graphite layer is advantageous for improving the overall performance of the battery, and comparative examples 1 to 5 show that the adjustment of the roughness of the graphite layer is advantageous for the performance of the battery, and that the optimal technical effect can be achieved within the scope of the present invention.
The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (13)

1. The preparation method of the negative electrode plate is characterized by comprising the following steps: immersing the negative electrode plate into an ester solution to obtain a negative electrode plate containing a carbonic ester organic layer, wherein the ester solution comprises vinylene carbonate;
the solvent in the ester solution also comprises any one or a combination of at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate;
the negative electrode piece is a metal lithium piece coated with a graphite layer;
in the metal lithium sheet coated with the graphite layer, the surface roughness of the graphite layer is 3-15 mu m.
2. The method according to claim 1, wherein the graphite layer is 5 to 100 μm thick in the graphite layer-coated metallic lithium sheet.
3. The method according to claim 1 or 2, wherein the particle size of graphite in the metallic lithium sheet coated with a graphite layer is less than 400 mesh.
4. The method of claim 1, wherein the concentration of solute in the ester-based solution is between 0.5 and 10mol/L.
5. The method of claim 4, wherein the concentration of vinylene carbonate in the ester solution is 0.1-2 mol/L.
6. The method according to claim 1, characterized in thatCharacterized in that the solute in the ester solution comprises LiNO 3 、KNO 3 、NaNO 3 、LiPF 2 、LiPF 6 、LiClO 4 、KClO 4 、KPF 6 、LiBF 4 、LiClO 4 、LiBOB、LiDFOB、LiAsF 6 、LiSbF 6 、LiCF 3 SO 3 、LiN(SO 2 CF 3 ) 2 、LiN(SO 2 C 2 F 5 ) 2 、LiN(SO 2 CF 3 ) 2 、LiN(SO 2 CF 3 ) 3 、LiB(CF 3 ) 4 Or LiBF 3 (C 2 F 5 ) Any one or a combination of at least two of these.
7. The method of claim 6, wherein the solute in the ester solution is LiNO 3 、LiPF 6 、LiBOB、LiCF 3 SO 3 、LiN(SO 2 CF 3 ) 2 And LiBF 3 (C 2 F 5 ) Any one or a combination of at least two of these.
8. The method of claim 1, wherein the negative electrode sheet is immersed in the ester solution for a period of time ranging from 1 to 48 hours.
9. The method of claim 1, wherein the negative electrode sheet is immersed in an ester solution and then dried.
10. The method of claim 9, wherein the drying is performed in a glove box.
11. The method of claim 9, wherein the drying temperature is 60 to 80 ℃.
12. A negative electrode sheet, characterized in that it is produced by the method of claim 1.
13. A solid-state battery comprising the negative electrode tab of claim 12.
CN202210261361.6A 2020-02-28 2020-02-28 Negative electrode plate, preparation method thereof and application thereof in solid-state battery Active CN114583110B (en)

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Publication number Priority date Publication date Assignee Title
CN108468042A (en) * 2018-03-23 2018-08-31 山东大学 A kind of method that fluorinated ethylene carbonate handles lithium metal and its application in solid state battery
CN110970598A (en) * 2019-12-23 2020-04-07 中航锂电技术研究院有限公司 Composite negative electrode of lithium battery, preparation method thereof and lithium battery comprising negative electrode

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CN109273704A (en) * 2017-07-18 2019-01-25 中国科学院上海硅酸盐研究所 A kind of lithium anode and preparation method thereof with high-ratio surface protective layer
WO2020067717A1 (en) * 2018-09-27 2020-04-02 주식회사 엘지화학 Negative electrode for all-solid-state battery and method for manufacturing same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108468042A (en) * 2018-03-23 2018-08-31 山东大学 A kind of method that fluorinated ethylene carbonate handles lithium metal and its application in solid state battery
CN110970598A (en) * 2019-12-23 2020-04-07 中航锂电技术研究院有限公司 Composite negative electrode of lithium battery, preparation method thereof and lithium battery comprising negative electrode

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