CN112103556A - Secondary battery and repairing method thereof - Google Patents

Secondary battery and repairing method thereof Download PDF

Info

Publication number
CN112103556A
CN112103556A CN202011235431.8A CN202011235431A CN112103556A CN 112103556 A CN112103556 A CN 112103556A CN 202011235431 A CN202011235431 A CN 202011235431A CN 112103556 A CN112103556 A CN 112103556A
Authority
CN
China
Prior art keywords
secondary battery
lithium
alloy
sodium
battery
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
CN202011235431.8A
Other languages
Chinese (zh)
Inventor
胡晨
金翼
王绥军
孙召琴
穆居易
黎可
于冉
刘家亮
刘超群
惠东
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
China Electric Power Research Institute Co Ltd CEPRI
Original Assignee
China Electric Power Research Institute Co Ltd CEPRI
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Electric Power Research Institute Co Ltd CEPRI filed Critical China Electric Power Research Institute Co Ltd CEPRI
Priority to CN202011235431.8A priority Critical patent/CN112103556A/en
Publication of CN112103556A publication Critical patent/CN112103556A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • 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
    • H01M10/4242—Regeneration of electrolyte or reactants
    • 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
    • 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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Secondary Cells (AREA)

Abstract

The invention discloses a secondary battery and a repairing method thereof, wherein the secondary battery comprises a shell; a positive electrode and a negative electrode which are separated by a diaphragm are arranged in the shell; electrolyte is filled between the anode and the diaphragm and between the cathode and the diaphragm; the negative electrode contains an alloy particle material. The invention adopts alloy lithium (or alloy sodium) to replace metal lithium (or sodium) as a lithium source (or a sodium source); mixing the alloy powder with a negative active material to prepare a negative pole piece containing the alloy powder, and matching the negative pole piece with a positive pole; more active Li can be supplemented by adding alloy containing lithium or sodium into the cathode of the secondary battery+Or Na+And the use of the alloy reduces the activity of metal lithium/sodium, and improves the safety performance of the battery.

Description

Secondary battery and repairing method thereof
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a secondary battery and a repairing method thereof.
Background
The secondary battery has excellent charge and discharge cycle characteristics, and thus is widely used in the fields of 3C electronic products, electric vehicles, energy storage, and the like. Secondary batteries (such as lithium ion batteries and sodium ion batteries) mainly comprise a positive electrode, a negative electrode, a diaphragm, electrolyte and a shell, wherein ions are respectively embedded/de-embedded and de-embedded/embedded on the positive electrode and the negative electrode, and the energy is stored and released by reciprocating through the diaphragm. The slower the capacity fade of the secondary battery, the better the cycle life performance thereof. The reason for the capacity degradation of the battery is various, such as that the formation of a solid electrolyte film (SEI film) on the surface of the negative electrode sheet during the first charge of the secondary battery consumes part of lithium from the positive electrode, resulting in the loss of lithium as a positive electrode material; during charging, metal (lithium or sodium) is precipitated from the negative electrode, and during the charge-discharge cycle of the secondary battery, side reactions occur, which cause decomposition of the electrolyte, decrease in conductivity, increase in internal resistance after the cycle, and decrease in capacity. Therefore, consumption of the electrolyte and active ions is one of the most significant causes of capacity fade and performance degradation of the battery.
In the prior art, for the problem of capacity fading, an important way is to pre-supplement lithium (or sodium ions) to the negative electrode, that is, to search a lithium source (or sodium source) from the outside of the positive electrode material to supplement the consumed lithium ions, so that the active ions consumed during the formation of the SEI film are supplemented, thereby improving the capacity of the lithium ion battery.
In order to compensate for the loss of active ions during charge and discharge overcharge, some methods have been reported in the patent and literature. Chinese patent application with application number 201210350770.X discloses a method for supplementing lithium to a lithium ion battery positive plate; the specific scheme is that at least one of n-hexane solution of n-butyllithium, n-hexane solution of tert-butyllithium and n-hexane solution of phenyllithium is adopted as an organic lithium solution, and the organic lithium solution is sprayed or dripped on the surface of the positive plate in an inert atmosphere, so that lithium ions in the organic lithium solution are reduced into metal lithium and are embedded into the positive plate. The n-butyl lithium, the tert-butyl lithium and the phenyl lithium can be dissolved in the n-hexane to form uniform solution, so that the spraying or dripping operation of the positive plate is facilitated. According to the method, the lithium is supplemented by a wet method, so that the lithium powder is distributed on the surface of the pole piece, and the uneven distribution of the lithium powder in the pole piece is avoided. Because the active metal lithium is directly added, the exothermic reaction between the active metal lithium and oxygen and moisture in the surrounding environment is easily caused, and the danger of combustion and explosion is caused; and the organic lithium source is a highly toxic substance, which is not favorable for practical production operation.
The prior art also has a pre-buried lithium supplement method; specifically, the metal lithium sheet is embedded into the battery, and an operator pastes the metal lithium sheet and the negative electrode of the battery together in advance in the process of preparing the battery, or directly adds metal lithium powder into the graphite negative electrode to provide a lithium source for later-stage battery pre-lithium. Chinese patent No. CN 1290209C also reports a "dry method" method for lithium supplement to a negative electrode, in which metallic lithium powder is directly added to a graphite negative electrode. Chinese patent No. CN 207558931U provides a method for bonding a lithium metal sheet and a negative electrode of a battery in advance. The lithium metal is abnormally active in the air and can be quickly oxidized and deteriorated in the air, and the lithium sheet in the air can also be violently reacted and ignited to cause danger. Meanwhile, in the actual operation process, the lithium metal powder must be isolated from air, so the operation is difficult and the large-scale production is not easy. In the lithium-embedded negative plate obtained by the method, the lithium powder is distributed in the middle of the negative material, and after the lithium powder is partially dissolved, the lithium powder is easily formed into an arc state and is electrically insulated from the negative electrode to form dead lithium, so that the dead lithium cannot participate in electrochemical reaction.
In the prior art, active lithium is directly added into an electrode active material to obtain a lithium-supplement negative plate. However, these organolithiums may cause combustion and explosion, and alkyllithiums are highly toxic substances, and thus have a great problem in terms of safety in production.
Disclosure of Invention
The invention aims to provide a secondary battery and a repairing method thereof, which solve the problems of unsafe lithium (sodium) supplement, high toxicity of a lithium (sodium) source and incapability of recovering the capacity performance of the battery in the later period in the prior art. In the later cycle period of the battery, electrolyte and additives are supplemented through the reserved electrolyte injection hole on the battery shell, and the SEI film damaged in the earlier cycle period of the battery is repaired according to a certain charging strategy, so that the capacity and the electrochemical performance of the battery are improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a secondary battery includes a case; a positive electrode and a negative electrode which are separated by a diaphragm are arranged in the shell; electrolyte is filled between the anode and the diaphragm and between the cathode and the diaphragm; the negative electrode contains alloy particle materials;
the shell is provided with a liquid injection hole for supplementing electrolyte;
after the secondary battery runs for a period of time, the supplementary liquid injected through the liquid injection hole consists of electrolyte and functional additives for repairing SEI films; the functional additive is composed of DTD, VC, FEC, LiDFOB and TTSPi.
The invention further improves the following steps: the secondary battery is a lithium battery; the alloy particle material is alloy lithium.
The invention further improves the following steps: the alloy lithium is specifically a lithium-aluminum alloy, a lithium-magnesium-aluminum alloy or a lithium-boron alloy.
The invention further improves the following steps: the lithium battery is specifically a lithium iron phosphate battery, a ternary lithium ion battery or a lithium titanate battery.
The invention further improves the following steps: the secondary battery is a sodium battery; the alloy particle material is alloy sodium.
The invention further improves the following steps: the alloy sodium is specifically a sodium-aluminum alloy or a sodium-magnesium alloy.
The invention further improves the following steps: the sodium battery is a Prussian blue-like sodium ion battery, an iron-based phosphate system sodium ion battery or a vanadium-based phosphate system sodium ion battery.
The invention further improves the following steps: d of the alloy particulate material50The particle size range is as follows: d is not more than 200nm50≤80μm。
The invention further improves the following steps: the weight of the alloy particle material is 1% -10% of the weight of the whole negative electrode material.
The invention further improves the following steps: the mass percentages of DTD, VC, FEC, LiDFOB and TTSPi in the supplementary liquid are respectively as follows: 0-6%, 0-12%: 0-10%, 0-8%, 0-6%, 0-13%.
A method of repairing a secondary battery, comprising:
supplementing a supplementary liquid to the secondary battery after the secondary battery operates for a period of time; the supplementary liquid consists of electrolyte and functional additives; the functional additive consists of DTD, VC, FEC, LiDFOB and TTSPi;
and performing reparative charging and discharging on the secondary battery after the supplement liquid is supplemented.
The invention further improves the following steps: the mass percentages of the DTD, the VC, the FEC, the LiDFOB and the TTSPi in the supplementary liquid are respectively as follows: 0-6%, 0-12%: 0-10%, 0-8%, 0-6%, 0-13%.
The invention further improves the following steps: the temperature for performing the repairability charging and discharging is 15-30 ℃.
The invention further improves the following steps: the charge-discharge cycle for the reparative charge-discharge is 1 or more times.
The invention further improves the following steps: the charge-discharge cycle for the reparative charge-discharge is 3 times or more.
The invention further improves the following steps: the charging method for performing reparative charging and discharging comprises the following steps: charging by adopting micro current of 0.01-0.1C.
The invention further improves the following steps: the charging method for performing reparative charging and discharging comprises the following steps: intermittent and stepped current charging is adopted.
The invention further improves the following steps: the intermittent and stepped current charging specifically comprises the following steps: the current is 0.01-0.1C in 1/3 time periods before the beginning; the current in the middle 1/3 time period is 0.1-0.3C; the current was 0.01C during the post 1/3 time period.
The invention further improves the following steps: the additive can function to repair the SEI film damaged during the cycle.
The invention further improves the following steps: the repairing charge and discharge is carried out, which is beneficial to removing interface damaged substances and repairing the damaged SEI film to be smoother, more compact and more complete.
Compared with the prior art, the invention has the following beneficial effects:
the invention adopts alloy lithium (or alloy sodium) to replace metal lithium (or sodium) as a lithium source (or a sodium source); mixing the alloy powder with a negative active material to prepare a negative pole piece containing the alloy powder, and matching the negative pole piece with a positive pole; more active Li can be supplemented by adding alloy containing lithium or sodium into the cathode of the secondary battery+Or Na+And the use of the alloy reduces the activity of metal lithium/sodium, and improves the safety performance of the battery.
Furthermore, the invention is provided with a liquid supplementing hole, and after the secondary battery runs for a period of time, supplementing liquid is supplemented into the secondary battery; the functional additive in the supplementary liquid is matched with a specific repairability charging and discharging method, so that the effects of enhancing the lithium ion conductivity of the battery and repairing a damaged SEI (solid electrolyte interphase) film are achieved, the battery capacity is remarkably improved, and the cycle life of the battery is prolonged.
Furthermore, the internal resistance of the battery repaired by the method is obviously reduced, and the cycle life is prolonged by 1500-2000 times (80% DOD).
Detailed Description
The following detailed description is exemplary in nature and is intended to provide further details of the invention. Unless otherwise defined, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention.
Example 1
The invention provides a secondary battery, comprising a shell; a positive electrode and a negative electrode which are separated by a diaphragm are arranged in the shell; electrolyte is filled between the positive electrode and the diaphragm and between the negative electrode and the diaphragm. And the shell is provided with a liquid injection hole capable of replenishing electrolyte into the shell, and the liquid injection hole is used for opening the liquid injection knot hole at the later cycle stage of the battery, discharging gas in the liquid injection knot hole, and adding a certain amount of electrolyte and functional additives.
The negative electrode is prepared by the following method: grinding the alloy material to obtain alloy material particles; d of alloy particles50The particle size range is as follows: d is not more than 200nm50Less than or equal to 80 mu m; uniformly mixing the alloy material particles and the negative electrode active substance to prepare an alloy negative electrode sheet; the weight of the alloy particles is 1% -10% of the weight of the whole negative electrode material. When the alloy material adopts lithium alloy, a lithium-containing alloy negative plate is obtained; when the alloy material adopts sodium alloy, the sodium-containing alloy negative plate is obtained. The lithium/sodium is pre-supplemented to the secondary battery through the alloy negative plate.
The invention adopts alloy lithium (or alloy sodium) to replace metal lithium (or sodium) as a lithium source (or sodium source), or compounds lithium/sodium by a carbon material; mixing the alloy powder with a negative active material to prepare a negative pole piece containing the alloy powder, and matching the negative pole piece with a positive pole; more active Li can be supplemented by adding alloy containing lithium or sodium into the cathode of the secondary battery+Or Na+And the use of the alloy reduces the activity of metal lithium/sodium, and improves the safety performance of the battery.
The alloy lithium (or alloy sodium) in the invention comprises lithium aluminum alloy, lithium magnesium aluminum alloy and lithium boron alloy (sodium aluminum alloy and sodium magnesium alloy).
The secondary battery in the present invention refers to a lithium ion battery and a sodium ion battery. The secondary battery system includes: lithium iron phosphate batteries, ternary lithium ion batteries, lithium titanate batteries; the system comprises a Prussian-like blue sodium ion battery, an iron-based phosphate system sodium ion battery and a vanadium-based phosphate system sodium ion battery.
The present invention also provides a method for repairing a secondary battery, comprising:
opening a liquid injection hole to inject supplementary liquid after the secondary battery runs for a period of time; the supplementary liquid consists of electrolyte and functional additives; after the battery is injected with liquid, repairable charging and discharging are carried out, the SEI film damaged in the earlier stage of the secondary battery is repaired, the battery capacity is recovered, and the electrochemical performance is improved.
The electrolyte component in the replenishing liquid is consistent with the electrolyte component originally filled in the battery; the functional additive can repair a damaged SEI film in a circulation process; the functional additive comprises: ethylene sulfate (DTD), Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), lithium difluorooxalato borate (liddob), and tris (trimethylsilyl) phosphite (TTSPi).
The mass percentages of the DTD, the VC, the FEC, the LiDFOB and the TTSPi in the supplementary liquid are respectively as follows: 0-6%, 0-12%: 0-10%, 0-8%, 0-6%, 0-13%.
The reparative charging and discharging method comprises the following steps: charging and discharging the secondary battery at 15-30 ℃; the number of charge and discharge cycles is more than 1 charge and discharge cycle; preferably, the number of charge/discharge cycles is 3 or more. The specific charging method comprises the following steps: charging by adopting micro current of 0.01C-0.1C, or charging by adopting intermittent or stepped current; the intermittent and stepped current charging specifically comprises the following steps: the current is 0.01-0.1C in 1/3 time periods before the beginning; the current in the middle 1/3 time period is 0.1-0.3C; the current was 0.01C during the post 1/3 time period.
Example 2
The invention relates to a method for repairing a secondary battery, which comprises the following steps: opening a liquid injection hole to inject supplementary liquid after the secondary battery runs for a period of time; the supplementary liquid consists of electrolyte and functional additives; after the battery is injected with liquid, repairable charging and discharging are carried out, the SEI film damaged in the earlier stage of the secondary battery is repaired, the battery capacity is recovered, and the electrochemical performance is improved.
The electrolyte component in the replenishing liquid is consistent with the electrolyte component originally filled in the battery; the functional additive can repair a damaged SEI film in a circulation process; the functional additive comprises: DTD, VC, FEC, LiDFOB, TTSPi. The mass percentages of the DTD, the VC, the FEC, the LiDFOB and the TTSPi in the supplementary liquid are respectively as follows: 1%, 10%: 5%, 8%, 6% and 2%.
The reparative charging and discharging method comprises the following steps: charging and discharging the secondary battery at 15-30 ℃; the number of charge and discharge cycles was 5.
Example 3
The difference between the present invention and the embodiment 2 is that the mass percentages of the added DTD, VC, FEC, LiDFOB and TTSPi in the supplementary liquid are respectively: 5% and 12%: 1%, 2%, 13%.
The reparative charging and discharging method comprises the following steps: charging and discharging the secondary battery at 15-30 ℃; the number of charge and discharge cycles was 3 charge and discharge cycles.
Example 4
The difference between the present invention and the embodiment 2 is that the mass percentages of the added DTD, VC, FEC, LiDFOB and TTSPi in the supplementary liquid are respectively: 6%, 1%: 5%, 1%, 4%, 6%.
The reparative charging and discharging method comprises the following steps: charging and discharging the secondary battery at 15-30 ℃; the number of charge and discharge cycles was 3 charge and discharge cycles.
Example 5
Example 5 differs from example 2 in that the specific method of charging is intermittent, stepped current charging: current was 0.01C for the initial pre-1/3 time period; the current is 0.1C in the middle 1/3 time period; the current was 0.01C during the post 1/3 time period.
Example 5
Example 5 differs from example 2 in that the specific method of charging is intermittent, stepped current charging: current was 0.05C for the initial pre-1/3 time period; the current is 0.1C in the middle 1/3 time period; the current was 0.01C during the post 1/3 time period.
Example 6
Example 6 differs from example 2 in that the specific method of charging is intermittent, stepped current charging: current was 0.01C for the initial pre-1/3 time period; the current was 0.3C for the middle 1/3 time period; the current was 0.01C during the post 1/3 time period.
Example 7
Example 7 differs from example 2 in that the specific method of charging is intermittent, stepped current charging: current was 0.1C for the initial pre-1/3 time period; the current was 0.2C for the middle 1/3 time period; the current was 0.01C during the post 1/3 time period.
The internal resistance of the battery repaired by the method is obviously reduced, and the cycle life is prolonged by 1500-2000 times (80% DOD).
It will be appreciated by those skilled in the art that the invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The embodiments disclosed above are therefore to be considered in all respects as illustrative and not restrictive. All changes which come within the scope of or equivalence to the invention are intended to be embraced therein.

Claims (18)

1. A secondary battery, comprising a case; a positive electrode and a negative electrode which are separated by a diaphragm are arranged in the shell; electrolyte is filled between the anode and the diaphragm and between the cathode and the diaphragm; the negative electrode contains alloy particle materials;
the shell is provided with a liquid injection hole for supplementing electrolyte;
after the secondary battery runs for a period of time, the supplementary liquid injected through the liquid injection hole consists of electrolyte and functional additives for repairing SEI films; the functional additive is composed of DTD, VC, FEC, LiDFOB and TTSPi.
2. The secondary battery according to claim 1, wherein the secondary battery is a lithium battery; the alloy particle material is alloy lithium.
3. A secondary battery according to claim 2, characterized in that the alloyed lithium is in particular a lithium aluminium alloy, a lithium magnesium aluminium alloy or a lithium boron alloy.
4. A secondary battery according to claim 2, characterized in that the lithium battery is in particular a lithium iron phosphate battery, a ternary lithium ion battery or a lithium titanate battery.
5. The secondary battery according to claim 1, wherein the secondary battery is a sodium battery; the alloy particle material is alloy sodium.
6. A secondary battery as claimed in claim 5, characterized in that the alloy sodium is in particular a sodium-aluminium alloy or a sodium-magnesium alloy.
7. The secondary battery according to claim 5, wherein the sodium battery is a Prussian-like blue sodium ion battery, an iron-based phosphate system sodium ion battery, or a vanadium-based phosphate system sodium ion battery.
8. The secondary battery according to claim 1, wherein D of the alloy particulate material50The particle size range is as follows: d is not more than 200nm50≤80μm。
9. The secondary battery of claim 1, wherein the weight of the alloy particle material is 1-10% of the total weight of the anode material.
10. The secondary battery of claim 1, wherein the mass percentages of DTD, VC, FEC, LiDFOB and TTSPi in the supplementary liquid are respectively as follows: 0-6%, 0-12%: 0-10%, 0-8%, 0-6%, 0-13%.
11. A method of repairing a secondary battery, comprising:
supplementing a supplementary liquid to the secondary battery after the secondary battery operates for a period of time; the supplementary liquid consists of electrolyte and functional additives for repairing SEI films; the functional additive consists of DTD, VC, FEC, LiDFOB and TTSPi;
and performing reparative charging and discharging on the secondary battery after the supplement liquid is supplemented.
12. The method for repairing a secondary battery according to claim 11, wherein the mass percentages of the DTD, VC, FEC, lidfeed, and TTSPi added to the replenishment solution are: 0-6%, 0-12%: 0-10%, 0-8%, 0-6%, 0-13%.
13. The method of claim 11, wherein the temperature at which the replenishing charge and discharge is performed is 15 ℃ to 30 ℃.
14. The method according to claim 11, wherein the charge-discharge cycle for the restorative charge-discharge is 1 or more times.
15. The method according to claim 11, wherein the charge-discharge cycle for the restorative charge-discharge is 3 times or more.
16. The method for repairing a secondary battery according to claim 11, wherein the charging method for performing the repairing charging and discharging includes: charging by adopting micro current of 0.01-0.1C.
17. The method for repairing a secondary battery according to claim 11, wherein the charging method for performing the repairing charging and discharging includes: intermittent and stepped current charging is adopted.
18. The method for repairing a secondary battery as claimed in claim 17, wherein the intermittent, step-current charging is specifically: the current is 0.01-0.1C in 1/3 time periods before the beginning; the current in the middle 1/3 time period is 0.1-0.3C; the current was 0.01C during the post 1/3 time period.
CN202011235431.8A 2020-11-09 2020-11-09 Secondary battery and repairing method thereof Pending CN112103556A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011235431.8A CN112103556A (en) 2020-11-09 2020-11-09 Secondary battery and repairing method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011235431.8A CN112103556A (en) 2020-11-09 2020-11-09 Secondary battery and repairing method thereof

Publications (1)

Publication Number Publication Date
CN112103556A true CN112103556A (en) 2020-12-18

Family

ID=73785165

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011235431.8A Pending CN112103556A (en) 2020-11-09 2020-11-09 Secondary battery and repairing method thereof

Country Status (1)

Country Link
CN (1) CN112103556A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114566725A (en) * 2022-02-18 2022-05-31 浙江晶科能源有限公司 Sodium-lithium hybrid battery system and control method

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101411007A (en) * 2006-03-30 2009-04-15 三洋电机株式会社 Lithium rechargeable battery and method for manufacturing the same
CN106170886A (en) * 2014-04-03 2016-11-30 3M创新有限公司 Additive agent electrolyte for lithium ion battery
CN106505249A (en) * 2016-12-15 2017-03-15 东莞市杉杉电池材料有限公司 A kind of lithium-ion battery electrolytes and the lithium ion battery containing the electrolyte
CN110611121A (en) * 2019-09-10 2019-12-24 宁德时代新能源科技股份有限公司 Electrolyte and lithium ion battery containing same
US20200028205A1 (en) * 2018-07-18 2020-01-23 Nanotek Instruments, Inc. Fast-chargeable lithium battery electrodes
CN111048830A (en) * 2018-10-12 2020-04-21 微宏动力***（湖州）有限公司 Nonaqueous electrolyte solution and lithium ion secondary battery

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101411007A (en) * 2006-03-30 2009-04-15 三洋电机株式会社 Lithium rechargeable battery and method for manufacturing the same
CN106170886A (en) * 2014-04-03 2016-11-30 3M创新有限公司 Additive agent electrolyte for lithium ion battery
CN106505249A (en) * 2016-12-15 2017-03-15 东莞市杉杉电池材料有限公司 A kind of lithium-ion battery electrolytes and the lithium ion battery containing the electrolyte
US20200028205A1 (en) * 2018-07-18 2020-01-23 Nanotek Instruments, Inc. Fast-chargeable lithium battery electrodes
CN111048830A (en) * 2018-10-12 2020-04-21 微宏动力***（湖州）有限公司 Nonaqueous electrolyte solution and lithium ion secondary battery
CN110611121A (en) * 2019-09-10 2019-12-24 宁德时代新能源科技股份有限公司 Electrolyte and lithium ion battery containing same

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114566725A (en) * 2022-02-18 2022-05-31 浙江晶科能源有限公司 Sodium-lithium hybrid battery system and control method
CN114566725B (en) * 2022-02-18 2024-02-09 浙江晶科能源有限公司 Sodium-lithium hybrid battery system and control method

Similar Documents

Publication Publication Date Title
CN101315994B (en) Formation method for lithium ion secondary battery
CN106797051A (en) For the solution of the prelithiation of lithium-ions battery
CN103988357A (en) Method for manufacturing nonaqueous electrolyte secondary battery
US11929509B2 (en) Metal lithium metal, supporting framework, and inorganic lithium compound, method for preparing the same, and electrode, battery, battery module, battery pack and apparatus comprising the same
CN113258139B (en) Pre-lithiation electrolyte and application thereof
CN105047916A (en) Method for improving electrochemical properties of lithium iron phosphate with copper/graphene
CN114614088B (en) Capacity compensation type electrolyte additive, preparation method and application thereof, and electrolyte and secondary battery containing additive
CN105655631A (en) Incombustible sodium secondary battery, electrolyte thereof and application of incombustible sodium secondary battery
CN107482247A (en) A kind of high-voltage lithium ion batteries
CN110994029B (en) Sulfone-based high-voltage electrolyte containing triphenylphosphine additives for lithium ion battery
CN111244530B (en) Electrolyte for alloy negative electrode material lithium battery and application thereof
Sun et al. Practical assessment of the energy density of potassium-ion batteries
WO2024109853A1 (en) Lithium-ion battery based on in-situ negative-electrode lithium supplementation, and preparation method therefor
US20010018151A1 (en) Electrolyte for lithium secondary battery
CN112103556A (en) Secondary battery and repairing method thereof
CN112271334B (en) Cathode film-forming additive for magnesium metal battery with metal magnesium as cathode material and application thereof
CN111224068A (en) Metal lithium cathode for lithium battery and lithium battery
CN113299897A (en) Na3V2(PO4)3Mixed ion full cell with @ C as anode material
CN116344943A (en) Lithium iron manganese phosphate battery electrolyte
CN114447323B (en) Lithium metal material with surface having phosphate layer, and preparation method and application thereof
CN115498176A (en) Lithium ion battery composite lithium supplement agent based on chemical combination reaction and application thereof
CN108172813A (en) A kind of composite positive pole and preparation method thereof
CN113921803A (en) Lithium supplementing method for lithium ion battery
CN113675469A (en) Carbonate electrolyte containing lithium nitrate, preparation method thereof and application thereof in lithium metal battery
CN111916828A (en) Lithium-sulfur battery electrolyte 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
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20201218