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CN112563454A - Method for pre-lithiation of negative pole piece - Google Patents

Method for pre-lithiation of negative pole piece Download PDF

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Publication number
CN112563454A
CN112563454A CN202011442831.6A CN202011442831A CN112563454A CN 112563454 A CN112563454 A CN 112563454A CN 202011442831 A CN202011442831 A CN 202011442831A CN 112563454 A CN112563454 A CN 112563454A
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China
Prior art keywords
pole piece
negative pole
prelithiation
lithiation
constant
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CN202011442831.6A
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Chinese (zh)
Inventor
崔大祥
阳靖峰
张芳
卢玉英
葛美英
张放为
王亚坤
焦靖华
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Priority to CN202011442831.6A priority Critical patent/CN112563454A/en
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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
    • H01M4/139—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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/44—Methods for charging or discharging
    • H01M10/446—Initial charging measures
    • 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
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a method for pre-lithiation of a negative pole piece, which comprises the steps of dissolving an aromatic hydrocarbon organic matter in an ether organic matter solvent to obtain a pre-lithiation precursor solution, then taking the negative pole piece as a working electrode and a lithium foil as a counter electrode, and carrying out discharging pre-lithiation in the pre-lithiation precursor solution by a constant current and constant voltage method. And after the constant-current constant-voltage discharge is finished, taking out the pole piece and drying the pole piece to obtain the pre-lithiated negative pole piece. The method has the advantages of simple process and capability of greatly improving the pre-lithiation effect of the negative pole piece.

Description

Method for pre-lithiation of negative pole piece
Technical Field
The invention relates to the field of lithium ion battery prelithiation, in particular to a method for prelithiation of a negative pole piece.
Background
In the first charge-discharge cycle of the lithium ion battery, a solid electrolyte membrane is generated on the surface of a negative electrode material, so that a large amount of lithium ions are consumed, and the capacity of the battery is greatly attenuated. Therefore, attention is paid to how to reduce the loss of lithium ions during the first charge and discharge of the battery negative electrode material. The pre-lithiation of the negative electrode material can enable the material to generate a solid electrolyte membrane or be embedded with lithium in advance before the first charge and discharge, so that the loss of lithium ions during the first charge and discharge is reduced, and the first charge and discharge efficiency is improved. However, in the prelithiation process, the conductive performance of the electrode surface is greatly reduced due to the formation of a solid electrolyte membrane, which further affects the charge and discharge effects of the lithium ion battery.
Disclosure of Invention
In order to avoid reducing the charging and discharging efficiency of the battery due to the generation of the solid electrolyte membrane, the invention aims to provide the method for pre-lithiating the negative pole piece, which has simple process and can improve the pre-lithiation effect of the negative pole piece.
The invention aims to provide the following scheme for realizing: a method for the prelithiation of a negative pole piece is disclosed, wherein aromatic hydrocarbon organic matters are dissolved in an ether organic solvent to obtain a prelithiation precursor solution, then the negative pole piece is used as a working electrode, a lithium foil is used as a counter electrode, the prelithiation is carried out in the prelithiation precursor solution by a constant current and constant voltage method, after the constant current and constant voltage discharge is finished, the pole piece is taken out and dried to obtain the prelithiation negative pole piece, and the method comprises the following steps:
the method comprises the following steps: dissolving aromatic hydrocarbon organic matters in an ether organic solvent to obtain a pre-lithiation precursor solution, wherein the concentration of the solution is 0.5M;
step two: putting the negative pole piece serving as a working electrode and the lithium foil serving as a counter electrode into the pre-lithiation precursor solution to obtain an aromatic hydrocarbon lithium salt solution;
step three: the negative pole piece is subjected to discharging pre-lithiation by a constant current and constant voltage method, wherein the constant current and constant voltage method is 0.1-0.01C, and the voltage is 0.3-0.5V (vs Li/Li)+）；
Step four: and drying the negative pole piece after the constant-current constant-voltage discharge is finished to obtain the pre-lithiated negative pole piece.
On the basis of the scheme, in the step one, the aromatic hydrocarbon organic matters are benzene, naphthalene, biphenyl and derivatives thereof; the ether organic solvent is one or two of tetrahydrofuran and ethylene glycol dimethyl ether.
Preferably, the aromatic hydrocarbon lithium salt is lithium biphenyl and its derivatives.
Preferably, the ether organic solvent is ethylene glycol dimethyl ether.
On the basis of the scheme, in the second step, the negative pole piece is made of one or more of silicon-based materials, hard carbon materials and graphite according to a conventional negative pole piece manufacturing method.
On the basis of the scheme, in the fourth step, the drying temperature is 40-90 ℃. Preferably, the drying temperature is 80 ℃.
Preferably, the constant voltage and the constant current have a current of 0.05C and a voltage of 0.45V.
The invention can effectively avoid the reduction of the charging and discharging efficiency of the battery due to the generation of the solid electrolyte membrane, has simple process and can greatly improve the pre-lithiation effect of the negative pole piece.
Drawings
FIG. 1 is a first charge-discharge curve of a half-cell of a pre-lithiated silicon negative electrode material prepared by the preparation method of the invention.
Detailed Description
Example 1:
a method for pre-lithiation of a negative pole piece is characterized in that aromatic hydrocarbon organic matters are dissolved in an ether organic solvent to obtain a pre-lithiation precursor solution, then the negative pole piece is used as a working electrode, a lithium foil is used as a counter electrode, discharging pre-lithiation is carried out in the pre-lithiation precursor solution by a constant current and constant voltage method, after constant current and constant voltage discharging is finished, the pole piece is taken out and dried to obtain the pre-lithiation negative pole piece, and the method comprises the following steps:
the method comprises the following steps: dissolving biphenyl in an ethylene glycol dimethyl ether solvent to obtain a pre-lithiation precursor solution, wherein the concentration of the solution is 0.5M;
step two: putting the negative pole piece serving as a working electrode and the lithium foil serving as a counter electrode into the pre-lithiation precursor solution to obtain an aromatic hydrocarbon lithium salt solution;
step three: the negative pole piece is subjected to discharging pre-lithiation by a constant current and constant voltage method, wherein the constant current and constant voltage method is 0.05C, and the voltage is 0.4V (vs Li/Li)+）；
Step four: and taking out the negative pole piece after the constant-current constant-voltage discharge is finished, and drying in vacuum at 80 ℃ to obtain the pre-lithiated negative pole piece.
Fig. 1 is a first charge-discharge curve diagram of a half-cell (a button cell is adopted as the half-cell, a lithium sheet is used as a counter electrode, and a conventional lithium battery electrolyte is used as the electrolyte) made of the pre-lithiated silicon negative electrode material prepared in the embodiment. The first charge-discharge efficiency of the pre-lithiated silicon oxide negative electrode material prepared in the embodiment is 91%.
Example 2:
a method for pre-lithiation of a negative pole piece is similar to that in example 1, and comprises the following steps:
the method comprises the following steps: dissolving biphenyl in tetrahydrofuran solvent to obtain a pre-lithiation precursor solution, wherein the concentration of the solution is 0.5M;
step two: putting a silicon monoxide negative pole piece serving as a working electrode and a lithium foil serving as a counter electrode into a pre-lithiation precursor solution;
step three: pre-lithiation is carried out on a silicon oxide cathode by adopting a constant voltage and constant current method, wherein the current is 0.01C, and the voltage is 0.4V (vs Li/Li)+）；
Step four: and taking out the negative pole piece after the constant-voltage constant-current discharge is finished, and drying in vacuum at 60 ℃ to obtain the pre-lithiated negative pole piece.
Example 3:
a method for pre-lithiation of a negative pole piece is similar to that in example 1, and comprises the following steps:
the method comprises the following steps: dissolving naphthalene in an ethylene glycol dimethyl ether solvent to obtain a pre-lithiation precursor solution, wherein the concentration of the solution is 0.5M;
step two: putting a hard carbon negative pole piece serving as a working electrode and a lithium foil serving as a counter electrode into a pre-lithiation precursor solution;
step three: performing pre-lithiation on the hard carbon cathode by adopting a constant voltage and constant current method, wherein the current is 0.05C, and the voltage is 0.4V (vs Li/Li)+）；
Step four: and taking out the negative pole piece after the constant-voltage constant-current discharge is finished, and drying the negative pole piece in vacuum at the temperature of 80 ℃ to obtain the pre-lithiated negative pole piece.
Example 4:
a method for pre-lithiation of a negative pole piece is similar to that in example 1, and comprises the following steps:
the method comprises the following steps: dissolving naphthalene in tetrahydrofuran solvent to obtain pre-lithiation precursor solution with the concentration of 0.5M;
step two: putting a graphite negative pole piece serving as a working electrode and a lithium foil serving as a counter electrode into the pre-lithiation precursor solution;
step three: pre-lithiation is carried out on a silicon oxide cathode by adopting a constant voltage and constant current method, wherein the current is 0.01C, and the voltage is 0.4V (vs Li/Li)+）；
Step four: and taking out the negative pole piece after the constant-voltage constant-current discharge is finished, and drying the negative pole piece in vacuum at the temperature of 80 ℃ to obtain the pre-lithiated negative pole piece.

Claims (8)

1. A method for the prelithiation of a negative pole piece is characterized in that aromatic hydrocarbon organic matters are dissolved in an ether organic solvent to obtain a prelithiation precursor solution, then the negative pole piece is used as a working electrode, a lithium foil is used as a counter electrode, the prelithiation is carried out in the prelithiation precursor solution by a constant current and constant voltage method, after the constant current and constant voltage discharge is finished, the pole piece is taken out and dried to obtain the prelithiation negative pole piece, and the method comprises the following steps:
the method comprises the following steps: dissolving aromatic hydrocarbon organic matters in an ether organic solvent to obtain a pre-lithiation precursor solution, wherein the concentration of the solution is 0.5M;
step two: putting the negative pole piece serving as a working electrode and the lithium foil serving as a counter electrode into the pre-lithiation precursor solution to obtain an aromatic hydrocarbon lithium salt solution;
step three: the negative pole piece is subjected to discharging pre-lithiation by a constant current and constant voltage method, wherein the constant current and constant voltage method is 0.1-0.01C, and the voltage is 0.3-0.5V (vs Li/Li)+）；
Step four: and drying the negative pole piece after the constant-current constant-voltage discharge is finished to obtain the pre-lithiated negative pole piece.
2. The method for prelithiation of a negative electrode tab of claim 1, wherein: in the first step, the aromatic hydrocarbon organic matters are benzene, naphthalene, biphenyl and derivatives thereof; the ether organic solvent is one or two of tetrahydrofuran and ethylene glycol dimethyl ether.
3. The method for prelithiation of a negative electrode tab of claim 1, wherein: in the second step, the negative pole piece is made of one or more of silicon-based materials, hard carbon materials and graphite according to a conventional negative pole piece manufacturing method.
4. The method for prelithiation of a negative electrode tab of claim 1, wherein: in the fourth step, the drying temperature is 40-90 ℃.
5. The method for prelithiation of a negative electrode tab of claim 4, wherein: the drying temperature was 80 ℃.
6. The method for prelithiation of a negative electrode tab of claim 2, wherein: the aromatic hydrocarbon lithium salt is lithium biphenyl and its derivative.
7. The method for prelithiation of a negative electrode tab of claim 2, wherein: the ether organic solvent is ethylene glycol dimethyl ether.
8. The method for prelithiation of a negative electrode tab of claim 1, wherein: the constant voltage and constant current has a current of 0.05C and a voltage of 0.45V.
CN202011442831.6A 2020-12-11 2020-12-11 Method for pre-lithiation of negative pole piece Pending CN112563454A (en)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105845894A (en) * 2016-05-04 2016-08-10 合肥国轩高科动力能源有限公司 Method and device for pre-lithiation of lithium ion battery negative pole piece
CN110120496A (en) * 2018-02-05 2019-08-13 武汉大学 A kind of negative electrode of lithium ion battery and its prelithiation methods and applications
WO2020009494A1 (en) * 2018-07-06 2020-01-09 주식회사 엘지화학 Negative electrode for lithium secondary battery, method for pre-lithiating same, and lithium secondary battery including same
WO2020085823A1 (en) * 2018-10-26 2020-04-30 주식회사 엘지화학 Method for manufacturing anode for lithium secondary battery
CN111261838A (en) * 2020-03-25 2020-06-09 上海电气集团股份有限公司 Method for pre-lithiation of silicon monoxide negative pole piece
CN111615769A (en) * 2018-03-07 2020-09-01 株式会社Lg化学 Method of making a negative electrode
CN111886722A (en) * 2019-01-31 2020-11-03 株式会社Lg化学 Method for prelithiating negative electrode of secondary battery
CN112038583A (en) * 2020-08-19 2020-12-04 上海纳米技术及应用国家工程研究中心有限公司 Preparation method for prelithiation of silicon monoxide negative pole piece

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105845894A (en) * 2016-05-04 2016-08-10 合肥国轩高科动力能源有限公司 Method and device for pre-lithiation of lithium ion battery negative pole piece
CN110120496A (en) * 2018-02-05 2019-08-13 武汉大学 A kind of negative electrode of lithium ion battery and its prelithiation methods and applications
CN111615769A (en) * 2018-03-07 2020-09-01 株式会社Lg化学 Method of making a negative electrode
WO2020009494A1 (en) * 2018-07-06 2020-01-09 주식회사 엘지화학 Negative electrode for lithium secondary battery, method for pre-lithiating same, and lithium secondary battery including same
WO2020085823A1 (en) * 2018-10-26 2020-04-30 주식회사 엘지화학 Method for manufacturing anode for lithium secondary battery
CN111886722A (en) * 2019-01-31 2020-11-03 株式会社Lg化学 Method for prelithiating negative electrode of secondary battery
CN111261838A (en) * 2020-03-25 2020-06-09 上海电气集团股份有限公司 Method for pre-lithiation of silicon monoxide negative pole piece
CN112038583A (en) * 2020-08-19 2020-12-04 上海纳米技术及应用国家工程研究中心有限公司 Preparation method for prelithiation of silicon monoxide negative pole piece

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Application publication date: 20210326