CN105206867A - Three-electrode system for lithium ion battery and preparation method thereof - Google Patents
Three-electrode system for lithium ion battery and preparation method thereof Download PDFInfo
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- CN105206867A CN105206867A CN201510648660.5A CN201510648660A CN105206867A CN 105206867 A CN105206867 A CN 105206867A CN 201510648660 A CN201510648660 A CN 201510648660A CN 105206867 A CN105206867 A CN 105206867A
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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
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/531—Electrode connections inside a battery casing
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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
-
- 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
Abstract
The invention provides a three-electrode system for a lithium ion battery. The three-electrode system comprises a working cell, an auxiliary cell and a sealing bag; the working cell and the auxiliary cell form a battery main body, which are superimposed in the vertical direction, and the battery main body is sealed in the sealing bag; both the working cell and the auxiliary cell respectively consist of a positive pole piece, a negative pole piece and a diaphragm which is arranged between the positive pole piece and the negative pole piece; the working cell also comprises a working positive tab and a working negative tab, and the working positive tab and the working negative tab are led out from the same side of the working cell; the auxiliary cell also comprises an auxiliary positive tab and an auxiliary negative tab, and both the auxiliary positive tab and the auxiliary negative tab are led out from the same side of the auxiliary cell; the working positive tab and the working negative tab are led out from one side of the sealing bag, and the auxiliary positive tab and the auxiliary negative tab are led out from the other opposite side of the sealing bag. The three-electrode system is simple in structure, good in sealing performance, high in accuracy and wide in practicability.
Description
Technical field
The present invention relates to field of lithium ion battery, particularly relate to a kind of lithium ion battery three-electrode system and preparation method thereof.
Background technology
At present, in the process of the chemical properties such as research lithium ion battery circulation, rate charge-discharge, high/low temperature electric discharge, storage, usual employing three-electrode system extracts positive pole in battery, negative pole relative to the electromotive force of reference electrode.By analyzing positive pole, negative pole relative to the potential change of reference electrode, obtaining positive pole, negative pole to the impact of battery performance, is adjustment positive pole, cathode pole piece Design and optimization bath composition, the chemical property provider then improving battery to.Therefore, provide the three-electrode system of stable reference electrode, reliable design most important.
Authorization Notice No. CN202949008U discloses a kind of three electrode assemblies of lithium ion battery, and length, the width of described positive pole, negative pole are 1 ~ 3cm; Reference electrode is metal lithium sheet, and diameter is 10 ~ 20mm, and thickness is 0.2cm; The lug of positive pole, negative pole and reference electrode is drawn from the not ipsilateral of housing respectively.This utility model good airproof performance, and eliminate the impact of solution internal resistance to the full extent.Shortcoming is: positive pole, cathode pole piece area is little, the number of plies is few, differs greatly with entity lithium ion battery especially high power capacity electrokinetic cell, and the referentiability in the chemical property feature and performance degradation of analysis entities lithium ion battery is more weak.In addition, the mode that this utility model adopts positive pole, barrier film, negative pole, barrier film, reference electrode to superpose in order is assembled.When having external force in manufacturing process, easily cause reference electrode to form overvoltage to the pole piece in residing region, even crush barrier film and cathode contact, cause test result abnormal.
Authorization Notice No. CN203039037U discloses a kind of three-electrode structure of lithium ion battery, described reference electrode is metal lithium sheet, be packaged in a sealing manner in airbag, effectively prevent reference electrode and contact with naked battery core and cause the pole piece overvoltage in region residing for reference electrode and inactivation and analyse lithium.Shortcoming is: one, will realize reference electrode and be sealed in airbag, so in manufacturing process, after fluid injection sealing, just can not carry out degasification to airbag, the gas causing battery preliminary filling to produce cannot be discharged and affect the chemical property of battery, therefore truly can not reflect the performance characteristics of battery.Two, described reference electrode is immersed in the electrolyte in airbag, means that in whole three-electrode structure, electrolyte is more.Too much electrolyte can cause solution internal resistance to increase, and the polarization caused by solution internal resistance is corresponding increase also, can not realize the accurate characterization to battery performance equally.
Summary of the invention
The problem to be solved in the present invention is to provide the lithium ion battery three-electrode system that a kind of structure is simple, good airproof performance, accuracy are high, practicality is wide.
For solving the problems of the technologies described above, the technical solution used in the present invention is: a kind of lithium ion battery three-electrode system, comprises work battery core, auxiliary battery core and packaging bag; Described work battery core and auxiliary battery core are presented down the structure stacked and are formed battery main body, and described battery main body is sealed in packaging bag; Described work battery core and auxiliary battery core form by positive plate, negative plate and the barrier film be positioned between positive plate, negative plate; Described work battery core also comprises work anode ear and work negative electrode lug, and described work anode ear and work negative electrode lug are drawn from work battery core the same side; Described auxiliary battery core also comprises auxiliary positive ear and auxiliary negative ear, and described auxiliary positive ear and auxiliary negative ear are drawn from auxiliary battery core the same side; Described work anode ear, work negative electrode lug are drawn from packaging bag side, and auxiliary positive ear, auxiliary negative ear are drawn from the relative opposite side of packaging bag.
Further, as reference electrode during the full electric state of the negative plate of described auxiliary battery core, traditional metal lithium sheet is replaced.
Further, described work positive plate, work negative plate and auxiliary positive sheet, auxiliary negative sheet measure-alike; Work anode ear, work negative electrode lug and auxiliary positive ear, the material of auxiliary negative ear and measure-alike.
Preferably, described work positive plate, auxiliary positive sheet are all LiFePO 4, cobalt acid lithium or nickel-cobalt lithium manganate material etc.; Described work negative plate, auxiliary negative sheet are all graphite, soft carbon or hard carbon material etc.
Present invention also offers and a kind ofly prepare the intermediate structure formed in lithium ion battery three-electrode system process, comprise outside above-mentioned technical characteristic, described packaging bag forms airbag in the region on battery main body side.The ratio of described airbag width and battery main body width is 1:3 ~ 1:1.The work anode ear of work battery core, the auxiliary positive ear of work negative electrode lug and auxiliary battery core, sealing place of auxiliary negative ear use identical end socket and packaging technology.
Another object of the present invention is to the preparation method that a kind of lithium ion battery three-electrode system is provided, comprise the following steps: (1) injects electrolyte in packaging bag, leave standstill 8 ~ 24h; (2) constant-current constant-voltage charging is carried out to work battery core and auxiliary battery core simultaneously; (3) degasification is carried out to the airbag of packaging bag and to packaging bag hot-pressing, edge-sealing, excision airbag.
Wherein with constant current 0.1 ~ 1.0C, constant-current constant-voltage charging is carried out to work battery core and auxiliary battery core in step (2); Charge cutoff voltage is 3.65 ~ 4.5V, specifically determines according to work battery core, the positive plate of auxiliary battery core, negative plate active material used; Constant-voltage phase cut-off current is 0.01 ~ 0.05C.Under this state, the negative plate of auxiliary battery core is reference electrode.After reference electrode is formed, encase auxiliary positive ear with insulating tape, in order to avoid forming short circuit between auxiliary positive ear and auxiliary negative ear.
Described in step (3), hot pressing temperature is 150 ~ 200 DEG C, and packaging bag seal width is 4 ~ 10mm, packaging bag seal inner distance battery main body 1 ~ 3mm.
The advantage that the present invention has and good effect are:
(1) in the chemical property feature and performance degradation of analysis entities lithium ion battery, there is very strong practicality.Described three-electrode system is not limited to the size of entity battery, as long as the positive plate of the positive plate of auxiliary battery core, negative plate and work battery core, negative plate are identical.In the electrochemical property test process such as circulation, rate charge-discharge, high/low temperature electric discharge, storage of entity lithium ion battery, this three-electrode system can Efficient Characterization positive pole, negative pole is relative to the potential change of reference electrode.
(2) test result is more reliable.Be embodied in: 1. avoid when to have external force in manufacturing process, using the metal lithium sheet of small size as reference electrode, overvoltage and inactivation formed to the pole piece in residing region and analyse lithium, it also avoid reference electrode simultaneously and crush barrier film and contact with negative plate.
2. the preliminary filling of described auxiliary battery core and work battery core arranges degasification operation after terminating, and eliminates the impact of gas on work battery core performance to the full extent.Free electrolyte can be extracted out in degasification operation simultaneously, and realizing free electrolyte in system does not increase; And the distance that the structure of auxiliary battery core and work battery core mounted on top shortens reference electrode and works between battery core positive plate, negative plate, reduce the polarization of solution internal resistance to work battery core positive plate, negative plate.
(3) this three-electrode system material used is all identical with actual battery, does not need additionally to prepare new material (such as metal lithium sheet).
Accompanying drawing explanation
Fig. 1 is the structural representation of lithium ion battery three-electrode system of the present invention
Fig. 2 is the schematic diagram preparing the intermediate structure formed in lithium ion battery three-electrode system process
Fig. 3 is work battery core positive plate charging and discharging curve figure
Fig. 4 is work battery core negative plate charging and discharging curve figure
Fig. 5 is that the DC internal resistance of work battery core positive plate and negative plate is with battery core SOC variation diagram
In figure:
1, battery main body; 2, packaging bag; 3, work anode ear; 4, work negative electrode lug; 5, auxiliary positive ear; 6, auxiliary negative ear; 7, airbag.
Embodiment
Embodiment 1 lithium ion battery three-electrode system
A kind of lithium ion battery three-electrode system, comprises work battery core, auxiliary battery core and packaging bag 2; Work battery core and auxiliary battery core are presented down the structure stacked and are formed battery main body 1, and battery main body 1 is sealed in packaging bag 2; Work battery core and auxiliary battery core form by positive plate, negative plate and the barrier film be positioned between positive plate, negative plate; Work battery core also comprises work anode ear 3 and work negative electrode lug 4, and work anode ear 3 and work negative electrode lug 4 are drawn from work battery core the same side; Auxiliary battery core also comprises auxiliary positive ear 5 and auxiliary negative ear 6, and auxiliary positive ear 5 and auxiliary negative ear 6 are drawn from auxiliary battery core the same side; Work anode ear 3, work negative electrode lug 4 are drawn from packaging bag 2 side, and auxiliary positive ear 5, auxiliary negative ear 6 are from packaging bag 2 opposite side extraction relatively.
Work positive plate, work negative plate and auxiliary positive sheet, auxiliary negative sheet measure-alike; Work anode ear, work negative electrode lug and auxiliary positive ear, the material of auxiliary negative ear and measure-alike.
Work positive plate, auxiliary positive sheet are all LiFePO 4, cobalt acid lithium or nickel-cobalt lithium manganate material etc.; Work negative plate, auxiliary negative sheet are all graphite, soft carbon or hard carbon material etc.
As reference electrode during the full electric state of the negative plate of auxiliary battery core, instead of traditional metal lithium sheet.
Embodiment 2
Present invention also offers and a kind ofly prepare the intermediate structure formed in lithium ion battery three-electrode system process, comprise outside the technical characteristic of embodiment 1, packaging bag 2 forms airbag 7 in the region on battery main body 1 side.The ratio of airbag 7 width and battery main body 1 width is 1:3 ~ 1:1.The work anode ear of work battery core, the auxiliary positive ear of work negative electrode lug and auxiliary battery core, sealing place of auxiliary negative ear use identical end socket and packaging technology.
The preparation method of embodiment 3 lithium ion battery three-electrode system
(1) in packaging bag, inject electrolyte, leave standstill 8 ~ 24h.
(2) constant-current constant-voltage charging is carried out to work battery core and auxiliary battery core simultaneously; With constant current 0.1 ~ 1.0C, constant-current constant-voltage charging is carried out to work battery core and auxiliary battery core; Charge cutoff voltage is 3.65 ~ 4.5V, specifically determines according to work battery core, the positive plate of auxiliary battery core, negative plate active material used; Constant-voltage phase cut-off current is 0.01 ~ 0.05C.Under this state, the negative plate of auxiliary battery core is reference electrode, after reference electrode is formed, encases auxiliary positive ear 5 with insulating tape, in order to avoid forming short circuit between auxiliary positive ear 5 and auxiliary negative ear 6.
(3) degasification is carried out to the airbag 7 of the packaging bag 2 of embodiment 2 and to packaging bag 2 hot-pressing, edge-sealing, excision airbag.Hot pressing temperature is 150 ~ 200 DEG C, and packaging bag 2 seal width is 4 ~ 10mm, packaging bag 2 seal inner distance battery main body 1 ~ 3mm.
Finally obtain embodiment 1 lithium ion battery three-electrode system.
Test experiments
Three-electrode system is tested: adopt a passage of charging/discharging apparatus to connect work anode ear respectively, with work negative electrode lug, discharge and recharge is carried out to work battery core, the two pairs of auxiliary electrical line balls connect work anode ear and auxiliary negative ear (reference electrode), work negative electrode lug and auxiliary negative ear (reference electrode) respectively, the automatic writing task anode ear of every 1 ~ 60s to work negative electrode lug voltage, work anode ear to reference electrode voltage, work negative electrode lug to reference electrode voltage.
With ferrous phosphate lithium battery cycle charge-discharge, (charge cutoff voltage is for 3.65V, discharge cut-off voltage is 2.0V) be example, Fig. 3, Fig. 4 are respectively the positive pole of work battery core and the negative pole charging and discharging curve in circulation initial stage, mid-term and later stage, can obtain positive pole, the negative pole deteriorated information in cyclic process.In addition, according to the computing formula of DC internal resistance=voltage difference/difference between current, three-electrode system of the present invention can also provide the DC internal resistance information of work battery core positive pole and negative pole, and Fig. 5 is the DC internal resistance situation of change of work battery core positive pole and negative pole under different SOC state.
Above embodiments of the invention have been described in detail, but described content being only preferred embodiment of the present invention, can not being considered to for limiting practical range of the present invention.All equalizations done according to the scope of the invention change and improve, and all should still belong within this patent covering scope.
Claims (10)
1. a lithium ion battery three-electrode system, is characterized in that: comprise work battery core, auxiliary battery core and packaging bag; Described work battery core and auxiliary battery core are presented down the structure stacked and are formed battery main body, and described battery main body is sealed in packaging bag; Described work battery core and auxiliary battery core form by positive plate, negative plate and the barrier film be positioned between positive plate, negative plate; Described work battery core also comprises work anode ear and work negative electrode lug, and described work anode ear and work negative electrode lug are drawn from work battery core the same side; Described auxiliary battery core also comprises auxiliary positive ear and auxiliary negative ear, and described auxiliary positive ear and auxiliary negative ear are drawn from auxiliary battery core the same side; Described work anode ear, work negative electrode lug are drawn from packaging bag side, and auxiliary positive ear, auxiliary negative ear are drawn from the relative opposite side of packaging bag.
2. lithium ion battery three-electrode system according to claim 1, is characterized in that: as reference electrode during the full electric state of the negative plate of described auxiliary battery core.
3. lithium ion battery three-electrode system according to claim 1, is characterized in that: described work positive plate, work negative plate and auxiliary positive sheet, auxiliary negative sheet measure-alike; Work anode ear, work negative electrode lug and auxiliary positive ear, the material of auxiliary negative ear and measure-alike.
4. lithium ion battery three-electrode system according to claim 1, is characterized in that: described work positive plate, auxiliary positive sheet are all LiFePO 4, cobalt acid lithium or nickel-cobalt lithium manganate material; Described work negative plate, auxiliary negative sheet are all graphite, soft carbon or hard carbon material.
5. lithium ion battery three-electrode system according to claim 1, is characterized in that: described packaging bag forms airbag in the region on battery main body side.
6. lithium ion battery three-electrode system according to claim 5, is characterized in that: the ratio of described airbag width and battery main body width is 1:3 ~ 1:1.
7. a preparation method for lithium ion battery three-electrode system, is characterized in that, comprises the following steps: (1) injects electrolyte in packaging bag, leaves standstill 8 ~ 24h; (2) constant-current constant-voltage charging is carried out to work battery core and auxiliary battery core simultaneously; (3) degasification is carried out to the airbag of packaging bag and to packaging bag hot-pressing, edge-sealing, excision airbag.
8. preparation method according to claim 7, is characterized in that: carry out constant-current constant-voltage charging with constant current 0.1 ~ 1.0C to work battery core and auxiliary battery core; Charge cutoff voltage is 3.65 ~ 4.5V; Constant-voltage phase cut-off current is 0.01 ~ 0.05C.
9. preparation method according to claim 7, is characterized in that: described hot pressing temperature is 150 ~ 200 DEG C, and packaging bag seal width is 4 ~ 10mm, packaging bag seal inner distance battery main body 1 ~ 3mm.
10. preparation method according to claim 1, is characterized in that: after auxiliary battery core is full of electricity, encases auxiliary positive ear with insulating tape.
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Cited By (4)
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| CN106842059A (en) * | 2017-03-07 | 2017-06-13 | 河海大学常州校区 | Lithium battery both positive and negative polarity electrochemical properties on-line monitoring method based on three electrode measurements |
| CN110350135A (en) * | 2018-04-06 | 2019-10-18 | 通用汽车环球科技运作有限责任公司 | The battery pack of battery battery core with asymmetric encapsulation and symmetrical current path |
| CN111082151A (en) * | 2019-12-25 | 2020-04-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for in-situ generation of lithium reference electrode in lithium ion soft package battery |
| CN114628769A (en) * | 2022-02-24 | 2022-06-14 | 四川国创成电池材料有限公司 | Four-electrode soft package lithium battery, and preparation method and test method thereof |
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| CN106842059A (en) * | 2017-03-07 | 2017-06-13 | 河海大学常州校区 | Lithium battery both positive and negative polarity electrochemical properties on-line monitoring method based on three electrode measurements |
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| CN111082151A (en) * | 2019-12-25 | 2020-04-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for in-situ generation of lithium reference electrode in lithium ion soft package battery |
| CN114628769A (en) * | 2022-02-24 | 2022-06-14 | 四川国创成电池材料有限公司 | Four-electrode soft package lithium battery, and preparation method and test method thereof |
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Application publication date: 20151230 |