CN108987836A - A kind of lithium ion battery three-electrode system and preparation method thereof - Google Patents
A kind of lithium ion battery three-electrode system and preparation method thereof Download PDFInfo
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- CN108987836A CN108987836A CN201810619087.9A CN201810619087A CN108987836A CN 108987836 A CN108987836 A CN 108987836A CN 201810619087 A CN201810619087 A CN 201810619087A CN 108987836 A CN108987836 A CN 108987836A
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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
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/48—Accumulators combined with arrangements for measuring, testing or indicating the condition of cells, e.g. the level or density of the electrolyte
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- 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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention discloses a kind of lithium ion battery three-electrode systems and preparation method thereof, the lithium ion battery three-electrode system includes battery core and shell, the battery core includes positive plate, negative electrode tab, diaphragm, reference electrode, short diaphragm, the reference electrode is molten lithium copper wire, the diaphragm is placed between positive plate and negative electrode tab, between the molten lithium partial insertion diaphragm and negative electrode tab of the molten lithium copper wire, the short diaphragm is placed between molten lithium copper wire and negative electrode tab, positive pole ear and multi-disc positive pole ear position are welded, negative lug and multi-disc negative pole ear position are welded, the battery core encapsulation is in the shell, electrolyte is full of in the shell, the other end copper wire of the molten lithium copper wire outside shell with reference electrode tab welding.The present invention is attached to copper wire surface using molten condition lithium and forms stable reference electrode, increases the stability of reference electrode current potential, not will cause the loss of battery core capacity, promotes the repeatability of the lithium ion battery of three-electrode structure.
Description
Technical field
The present invention is a kind of technical field of lithium ion more particularly to a kind of lithium ion battery three-electrode system and its system
Preparation Method.
Background technique
Lithium ion battery is because having high-energy density, high voltage platform, small size, low self-discharge, long-life, memoryless effect
3C industry, new energy power industry, energy storage industry etc. should be widely used in the advantages such as environmental-friendly.City at present
There is the lithium ion battery of the types such as rectangular aluminum hull, Soft Roll, cylinder on field, be widely used in 3C battery, in power, energy storage, army
The industries such as work are also by large-scale application.
Lithium ion battery is a kind of chemical cell, and electrochemical reaction occurs for the internal moment in charge and discharge process, and inside is deposited
Electrolyte consumption, SEI film (solid electrolyte film) generate, cathode analyses lithium etc., this just needs a kind of in situ detection inside battery
The method of electrochemical reaction, three-electrode method introduce reference electrode, can be to inside battery anodic potentials, cathode potential and impedance
Carry out in-situ monitoring.
Chinese patent CN202949008U discloses a kind of three electrode assemblies of lithium ion battery, the length of anode, cathode
Degree, width are 1~3cm；Reference electrode is metal lithium sheet, and diameter is 10~20mm, with a thickness of 0.2cm；Anode, cathode and ginseng
Tab than electrode is drawn from the not ipsilateral of shell respectively.During battery is made when heat cold pressing, high-temperature clamp chemical conversion, two envelopes
Diaphragm is easy to crumple, and the pole piece for easily leading to region locating for reference electrode forms over-voltage, or even crushing diaphragm causes battery core short-circuit.Electricity
Pond in charge and discharge process, the corresponding negative electrode tab of reference electrode can not embedding lithium, capacitance loss is larger.
Chinese patent CN105470577A discloses a kind of three electrode assembling method of flexible packing lithium ion battery, reference electricity
Extremely spun gold, filamentary silver or platinum filament, wire exposed in this way can cause certain interference to electric signal in the electrolytic solution, cost compared with
It is high.
Chinese patent CN107293778A discloses a kind of three-electrode battery and preparation method thereof, and reference electrode is copper
Silk plates lithium for metal lithium platingactive on copper wire surface by micro-current, but electroplating process requires height to equipment precision, range, and
It is more unstable to plate lithium, it is less reproducible, lithium is plated in charge and discharge process to be easy to peel off and cause reference electrode current potential unstable.
Summary of the invention
The purpose of the present invention is to provide a kind of lithium ion battery three-electrode systems and preparation method thereof, solve above-mentioned background
The problem of middle proposition.
To achieve the above object, the invention provides the following technical scheme:
A kind of lithium ion battery three-electrode system, including battery core and shell, the battery core include positive plate, negative electrode tab, every
Film, reference electrode, short diaphragm, the reference electrode are molten lithium copper wire, and the diaphragm is placed between positive plate and negative electrode tab,
Between the molten lithium partial insertion diaphragm and negative electrode tab of the molten lithium copper wire, the short diaphragm be placed in molten lithium copper wire and negative electrode tab it
Between, positive pole ear and multi-disc positive pole ear position are welded, and negative lug and multi-disc negative pole ear position are welded, and the battery core is encapsulated in outer
In shell, electrolyte is full of in the shell.
Further, the diameter of the molten lithium copper wire is 20~50um.
Further, short diaphragm length is 5~7cm, and width is 2~3cm.
Further, the bare copper wire end of the molten lithium copper wire outside shell with reference electrode tab welding.
Further, the shell is aluminum plastic film or aluminum hull.
A kind of preparation method of lithium ion battery three-electrode system, which comprises the following steps:
S1: by one end of copper wire to be processed, about 4~6cm is placed in 60~120min of reaction in the concentrated sulfuric acid, to outer oxide
Object is corroded completely, and copper wire is exposed when outer, is cleaned 3~5 times with deionized water and acetone respectively, makes exposed copper silk remained on surface
The concentrated sulfuric acid clean up；
S2: lithium metal is melted in the resistance to height of 50-200ml in the glove box of isolation air and the pure argon environment of moisture
In warm ptfe autoclave liner, the 4~6cm of copper wire one end handled well is inserted into 1~2 in molten lithium by 180 DEG C of heat preservations
Second, due to environment temperature rapid drawdown after slowly extracting, molten lithium is attached to copper wire surface and forms stable and firm lithium metal, will melt
Lithium copper wire is sealed；
S3: the molten lithium of short diaphragm and copper wire is being partially disposed in naked battery core just in the fluid injection room that control dew point is -40 DEG C
Between pole piece and negative electrode tab, another part is placed on the outside of naked battery core, and naked battery core is put into shell and injects electrolyte；
S4: the copper wire and reference electrode tab welding being placed on the outside of battery, reference electrode tab are fixed on shell with adhesive tape
Surface, reference electrode tab carry out bending tilting, obtain lithium ion battery three-electrode system.
Further, the length that lithium end is melted in the molten lithium copper wire is 4~6cm.
The present invention introduces the copper wire optimized as reference electrode collector in lithium ion battery, does not influence lithium ion and exists
Transmission between anode and cathode, will not interfere electric signal, and cost of manufacture is cheap, improve contact of the lithium metal with copper wire and ask
Topic improves reference electrode potential stability, promotes the repeatability of lithium ion battery.
Compared with prior art, the beneficial effects of the present invention are:
Copper wire surface is attached to using molten condition lithium and forms stable reference electrode, increases the steady of reference electrode current potential
Qualitative, superfine copper wire guarantees that lithium ion in the transmission of positive and negative interpolar, not will cause the loss of battery core capacity, to lithium ion battery again
Anodic potentials, cathode potential carry out in-situ monitoring in use process, hence it is evident that improve the accuracy of detection, detection efficiency is high, is promoted
The repeatability of the lithium ion battery of three-electrode structure.
Detailed description of the invention
Fig. 1 is lithium ion battery three-electrode system structure front schematic view.
Fig. 2 is lithium ion battery three-electrode system texture edge schematic diagram.
In figure, 1- positive pole ear, 2- negative lug, 3- melts lithium copper wire, 4- reference electrode tab, 5- negative electrode tab, 6- it is short every
Film, 7- diaphragm, 8- positive plate, 9- electrolyte, 10- shell.
Fig. 3 is three-electrode system lithium ion battery charging voltage-time plot.
In figure, the n- reference potential curve 1 of 1 three electrode lithium ion battery of embodiment, 2 three electrode lithium ion battery of embodiment
N- reference potential curve 2,1 three electrode negative electrode of lithium ion battery of embodiment-reference potential curve 3,2 three electrode lithium of embodiment from
Sub- battery cathode-reference potential curve 4
Specific embodiment
Example 1
A kind of lithium ion battery three-electrode system includes battery core and shell 10, the battery core include positive plate 8, negative electrode tab 5,
Molten lithium copper wire 3, short diaphragm 6, diaphragm 7, the diaphragm 7 are placed between positive plate 8 and negative electrode tab 5, the molten lithium of the molten lithium copper wire 3
Between partial insertion diaphragm 7 and negative electrode tab 5, the short diaphragm 6 is placed between molten lithium copper wire 3 and negative electrode tab 5, the positive pole ear
1 welds with multi-disc positive pole ear position, and the negative lug 2 is welded with multi-disc negative pole ear position, and the battery core is packaged in described outer
In shell 10, filling electrolyte 9 in shell, the other end of the molten lithium copper wire 3 is welded outside shell 10 with reference electrode tab 4.
The diameter of molten lithium copper wire 3 is 20um, melts lithium partial-length 4cm, in order to prevent reference electrode and cathode short circuit, it is short every
Film length is 5cm, width 2cm.
A kind of preparation method of lithium ion battery three-electrode system, comprising the following steps:
S1: being placed in 60~120min of reaction in the concentrated sulfuric acid for one end of copper wire to be processed, completely rotten to outer oxide object
Erosion, copper wire is exposed when outer, is cleaned 3~5 times with deionized water and acetone respectively, keeps the exposed copper silk concentrated sulfuric acid remained on surface clear
Wash clean.
S2: lithium metal is melted in the resistance to height of 50-200ml in the glove box of isolation air and the pure argon environment of moisture
In warm ptfe autoclave liner, 180 DEG C heat preservation, by the copper wire one end handled well be inserted into molten lithium in 1~2 second, slowly
Due to environment temperature rapid drawdown after extraction, molten lithium is attached to copper wire surface and forms stable and firm lithium metal, by molten lithium copper wire
It is sealed.
S3: control dew point be in -40 DEG C of fluid injection room by the molten lithium of short diaphragm and copper wire be partially disposed in naked battery core every
Between film and negative electrode tab, naked battery core is put into shell and injects electrolyte, and another part of molten lithium copper wire is placed in outer side of shell.
S4: the copper wire and reference electrode tab welding being placed on the outside of battery, reference electrode tab are fixed on shell with adhesive tape
Surface, reference electrode tab carry out bending tilting, obtain lithium ion battery three-electrode system.
Embodiment 2
A kind of lithium ion battery three-electrode system includes battery core and shell 10, the battery core include positive plate 8, negative electrode tab 5,
Molten lithium copper wire 3, short diaphragm 6, diaphragm 7, the diaphragm 7 are placed between positive plate 8 and negative electrode tab 5, the molten lithium of the molten lithium copper wire 3
Between partial insertion diaphragm 7 and negative electrode tab 5, the short diaphragm 6 is placed between molten lithium copper wire 3 and negative electrode tab 5, the positive pole ear
1 welds with multi-disc positive pole ear position, and the negative lug 2 is welded with multi-disc negative pole ear position, and the battery core is packaged in described outer
In shell 10, filling electrolyte 9 in shell, the other end of the molten lithium copper wire 3 is welded outside shell 10 with reference electrode tab 4.
The diameter of molten lithium copper wire 3 is 50um, melts lithium partial-length 6cm, in order to prevent reference electrode and cathode short circuit, it is short every
Film length is 7cm, width 3cm.
Preparation method is same as Example 1.
Embodiment 3
A kind of lithium ion battery three-electrode system includes battery core and shell 10, the battery core include positive plate 8, negative electrode tab 5,
Molten lithium copper wire 3, short diaphragm 6, diaphragm 7, the diaphragm 7 are placed between positive plate 8 and negative electrode tab 5, the molten lithium of the molten lithium copper wire 3
Between partial insertion diaphragm 7 and negative electrode tab 5, the short diaphragm 6 is placed between molten lithium copper wire 3 and negative electrode tab 5, the positive pole ear
1 welds with multi-disc positive pole ear position, and the negative lug 2 is welded with multi-disc negative pole ear position, and the battery core is packaged in described outer
In shell 10, filling electrolyte 9 in shell, the other end of the molten lithium copper wire 3 is welded outside shell 10 with reference electrode tab 4.
The diameter of molten lithium copper wire 3 is 40um, melts lithium partial-length 5cm, in order to prevent reference electrode and cathode short circuit, it is short every
Film length is 6cm, width 2.5cm.
Preparation method is same as Example 1.
It is tested with lithium battery test cabinet and two piece of three electrode lithium ion battery of embodiment 1 and embodiment 2 charges, used
Multichannel data recorder collects anode-reference, cathode-reference current potential, as shown in Fig. 2, two piece of three electrode lithium ion battery
Anode-reference (curve 1 and curve 2), cathode-reference (curve 3 and curve 4) potential curve have higher registration, it was demonstrated that
The lithium ion battery repeatability of the invention is high.
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, though
So the present invention has been disclosed as a preferred embodiment, and however, it is not intended to limit the invention, any technology people for being familiar with this patent
Member without departing from the scope of the present invention, when the technology contents using above-mentioned prompt make it is a little change or be modified to
The equivalent embodiment of equivalent variations, but anything that does not depart from the technical scheme of the invention content, it is right according to the technical essence of the invention
Any simple modification, equivalent change and modification made by above embodiments, in the range of still falling within the present invention program.
Claims (7)
1. a kind of lithium ion battery three-electrode system, including battery core and shell, which is characterized in that the battery core include positive plate,
Negative electrode tab, diaphragm, reference electrode, short diaphragm, the reference electrode are molten lithium copper wire, and the diaphragm is placed in positive plate and bears
Between pole piece, between the molten lithium partial insertion diaphragm and negative electrode tab of the molten lithium copper wire, the short diaphragm be placed in molten lithium copper wire and
Between negative electrode tab, positive pole ear and multi-disc positive pole ear position are welded, and negative lug and multi-disc negative pole ear position are welded, the battery core
Encapsulation in the shell, is full of electrolyte in the shell.
2. lithium ion battery three-electrode system according to claim 1, which is characterized in that the diameter of the molten lithium copper wire is
20~50um.
3. lithium ion battery three-electrode system according to claim 1, which is characterized in that the short diaphragm length be 5~
7cm, width are 2~3cm.
4. lithium ion battery three-electrode system according to claim 1, which is characterized in that the bare copper wire of the molten lithium copper wire
End outside shell with reference electrode tab welding.
5. lithium ion battery three-electrode system according to claim 1, which is characterized in that the shell is aluminum plastic film or aluminium
Shell.
6. a kind of preparation method of lithium ion battery three-electrode system as described in claim 1, which is characterized in that including following
Step:
S1: being placed in 60~120min of reaction in the concentrated sulfuric acid for one end of copper wire to be processed, be corroded completely to outer oxide object, copper
Silk is exposed when outer, is cleaned 3~5 times with deionized water and acetone respectively, keeps the concentrated sulfuric acid cleaning remained on surface of exposed copper silk dry
Only；
S2: the high temperature resistant that lithium metal is melted in 50-200ml is gathered in the glove box of isolation air and the pure argon environment of moisture
In tetrafluoroethene inner liner of reaction kettle, the copper wire one end handled well is inserted into molten lithium 1~2 second, is slowly extracted by 180 DEG C of heat preservations
Afterwards due to environment temperature rapid drawdown, molten lithium is attached to copper wire surface and forms stable and firm lithium metal, and molten lithium copper wire is sealed
It saves；
S3: the molten lithium of short diaphragm and copper wire is partially disposed in the diaphragm of battery core in the fluid injection room that control dew point is -40 DEG C and is born
Between pole piece, battery core is put into shell and injects electrolyte, and another part of molten lithium copper wire is placed in outer side of shell；
S4: the copper wire and reference electrode tab welding being placed on the outside of battery, reference electrode tab are fixed on case surface with adhesive tape,
Reference electrode tab carries out bending tilting, obtains lithium ion battery three-electrode system.
7. the preparation method of lithium ion battery three-electrode system according to claim 6, which is characterized in that the molten lithium copper
The length that lithium end is melted in silk is 4~6cm.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109687033A (en) * | 2018-12-28 | 2019-04-26 | 蜂巢能源科技有限公司 | Multi-electrode lithium battery preparation method and multi-electrode lithium battery and lithium battery cathode plate multiple spot potential measurement method |
| CN110061299A (en) * | 2019-05-08 | 2019-07-26 | 上海航天电源技术有限责任公司 | A kind of method of lithium ion cell electrode pre- embedding lithium in situ |
| CN110797569A (en) * | 2019-10-31 | 2020-02-14 | 深圳新恒业电池科技有限公司 | Four-electrode lithium ion battery and potential measuring method thereof |
| CN111063939A (en) * | 2019-12-19 | 2020-04-24 | 东莞维科电池有限公司 | Three-electrode battery and preparation method thereof |
| CN111509304A (en) * | 2020-04-27 | 2020-08-07 | 惠州亿纬锂能股份有限公司 | Lithium ion three-electrode and preparation method and application thereof |
| CN112430833A (en) * | 2019-08-26 | 2021-03-02 | 郑州深澜动力科技有限公司 | Metal lithium plating method used as reference electrode of three-electrode lithium ion battery |
| CN112444753A (en) * | 2020-11-11 | 2021-03-05 | 北京理工大学 | Impedance test method for lithium analysis detection of lithium ion battery |
| CN113839111A (en) * | 2020-06-08 | 2021-12-24 | 华为技术有限公司 | Lithium ion battery and terminal equipment comprising same |
| WO2022056787A1 (en) * | 2020-09-17 | 2022-03-24 | 华为数字能源技术有限公司 | Three-electrode battery and energy storage system |
| CN115863785A (en) * | 2023-02-09 | 2023-03-28 | 楚能新能源股份有限公司 | Lithium ion battery and method for monitoring lithium deposition |
| CN116072813A (en) * | 2021-11-02 | 2023-05-05 | 宁德时代新能源科技股份有限公司 | Method for producing reference electrode, method for producing three-electrode cell, three-electrode cell |
| CN117810578A (en) * | 2023-12-11 | 2024-04-02 | 三一红象电池有限公司 | Sodium ion battery reference electrode, preparation method thereof and three-electrode battery |
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| CN110061299A (en) * | 2019-05-08 | 2019-07-26 | 上海航天电源技术有限责任公司 | A kind of method of lithium ion cell electrode pre- embedding lithium in situ |
| CN112430833A (en) * | 2019-08-26 | 2021-03-02 | 郑州深澜动力科技有限公司 | Metal lithium plating method used as reference electrode of three-electrode lithium ion battery |
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| CN111063939A (en) * | 2019-12-19 | 2020-04-24 | 东莞维科电池有限公司 | Three-electrode battery and preparation method thereof |
| CN111509304A (en) * | 2020-04-27 | 2020-08-07 | 惠州亿纬锂能股份有限公司 | Lithium ion three-electrode and preparation method and application thereof |
| CN111509304B (en) * | 2020-04-27 | 2023-06-30 | 惠州亿纬锂能股份有限公司 | Lithium ion three-electrode and preparation method and application thereof |
| CN113839111A (en) * | 2020-06-08 | 2021-12-24 | 华为技术有限公司 | Lithium ion battery and terminal equipment comprising same |
| WO2022056787A1 (en) * | 2020-09-17 | 2022-03-24 | 华为数字能源技术有限公司 | Three-electrode battery and energy storage system |
| CN112444753A (en) * | 2020-11-11 | 2021-03-05 | 北京理工大学 | Impedance test method for lithium analysis detection of lithium ion battery |
| CN116072813A (en) * | 2021-11-02 | 2023-05-05 | 宁德时代新能源科技股份有限公司 | Method for producing reference electrode, method for producing three-electrode cell, three-electrode cell |
| WO2023078043A1 (en) * | 2021-11-02 | 2023-05-11 | 宁德时代新能源科技股份有限公司 | Method for preparing reference electrode, reference electrode, method for preparing three-electrode battery, and three-electrode battery |
| CN115863785A (en) * | 2023-02-09 | 2023-03-28 | 楚能新能源股份有限公司 | Lithium ion battery and method for monitoring lithium deposition |
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