CN113948758A - Battery and battery repairing method - Google Patents
Battery and battery repairing method Download PDFInfo
- Publication number
- CN113948758A CN113948758A CN202111163985.6A CN202111163985A CN113948758A CN 113948758 A CN113948758 A CN 113948758A CN 202111163985 A CN202111163985 A CN 202111163985A CN 113948758 A CN113948758 A CN 113948758A
- Authority
- CN
- China
- Prior art keywords
- battery
- packaging body
- metal layer
- positive electrode
- corrosion
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000007797 corrosion Effects 0.000 claims abstract description 71
- 238000005260 corrosion Methods 0.000 claims abstract description 71
- 238000004806 packaging method and process Methods 0.000 claims abstract description 62
- 229910052751 metal Inorganic materials 0.000 claims abstract description 58
- 239000002184 metal Substances 0.000 claims abstract description 58
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 43
- 230000002687 intercalation Effects 0.000 claims abstract description 37
- 238000009830 intercalation Methods 0.000 claims abstract description 37
- 239000010410 layer Substances 0.000 claims description 61
- 238000009413 insulation Methods 0.000 claims description 19
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- 239000012793 heat-sealing layer Substances 0.000 claims description 11
- 239000011241 protective layer Substances 0.000 claims description 11
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 230000008439 repair process Effects 0.000 claims description 8
- -1 polypropylene Polymers 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000002985 plastic film Substances 0.000 description 14
- 229920006255 plastic film Polymers 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 10
- 238000010586 diagram Methods 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000003292 glue Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 230000005684 electric field Effects 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000005536 corrosion prevention Methods 0.000 description 2
- 238000012217 deletion Methods 0.000 description 2
- 230000037430 deletion Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 206010016766 flatulence Diseases 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 238000012858 packaging process Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 208000018999 crinkle Diseases 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Images
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
- H01M10/058—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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/425—Structural combination with electronic components, e.g. electronic circuits integrated to the outside of the casing
-
- 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
- H01M50/10—Primary casings; Jackets or wrappings
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Connection Of Batteries Or Terminals (AREA)
Abstract
The invention provides a battery and a battery repairing method. The invention provides a battery in a first aspect, which comprises a battery cell, a packaging body and a positive electrode tab, wherein the battery cell is sealed in the packaging body, one end of the positive electrode tab is connected with the battery cell, and the other end of the positive electrode tab is positioned outside the packaging body; the packaging body comprises a metal layer, N resistance elements are connected between the positive pole lug and the metal layer, N is a positive integer greater than or equal to 1, and the total resistance of the N resistance elements is less than or equal to 50M omega. According to the invention, the resistance element with the total resistance of less than or equal to 50 MOmega is connected between the positive electrode lug and the metal layer, so that lithium intercalation corrosion of the battery can be effectively prevented.
Description
Technical Field
The invention relates to a battery and a battery repairing method, and relates to the technical field of electrochemistry.
Background
The battery is a device capable of converting chemical energy into electric energy, and comprises an electric core and a packaging body for sealing the electric core, wherein in the use process of the battery, the most common failure mode is that the packaging body generates lithium embedding corrosion, and then the problems of liquid leakage, gas expansion, packaging damage and the like are caused, so that the battery fails. For consumer products, although only a single battery cell is corroded, the product is usually in direct contact with personnel, such as a mobile phone, a notebook computer, a bracelet, a watch, an earphone and the like, and the battery cell corrosion, liquid leakage and flatulence can bring poor use experience to customers; for power products, a module of the power product is usually formed by connecting dozens of large electric cores in series-parallel connection, and the corrosion, liquid leakage and gas expansion of one electric core can cause the failure of the whole model, so that the loss is extremely high. Therefore, how to avoid lithium intercalation corrosion of the package in the battery becomes one of the research hotspots in the field.
Disclosure of Invention
The invention provides a battery, which is used for preventing lithium intercalation corrosion of the battery.
The invention also provides a method for repairing the battery with lithium intercalation corrosion, which can repair the battery with lithium intercalation corrosion.
The invention provides a battery in a first aspect, which comprises a battery cell, a packaging body and a positive electrode tab, wherein the battery cell is sealed in the packaging body, one end of the positive electrode tab is connected with the battery cell, and the other end of the positive electrode tab is positioned outside the packaging body;
the packaging body comprises a metal layer, N resistance elements are connected between the positive pole lug and the metal layer, N is a positive integer greater than or equal to 1, and the total resistance of the N resistance elements is less than or equal to 50M omega.
In the battery, the total resistance of the N resistance elements is equal to or greater than 0.1 Ω.
As in the above battery, the total resistance of the N resistance elements is 1M Ω.
As in the above battery, the N resistance elements are connected in parallel or in series between the positive electrode tab and the metal layer.
According to the battery, the outer surfaces of the N resistance elements are coated with the adhesive paper, and the adhesive paper is used for isolating the resistance elements from being in contact with an external circuit.
According to the battery, the packaging body comprises the heat sealing layer, the metal layer and the protective layer which are sequentially stacked, the heat sealing layer is located on one side, close to the battery core, of the metal layer, and the protective layer is located on one side, far away from the battery core, of the metal layer.
As in the above cell, the metal layer comprises one or both of aluminum and steel.
As in the above cell, the heat seal layer comprises polypropylene and its composite.
As in the above battery, the protective layer comprises a composite of polyamide and polyethylene terephthalate.
In a second aspect, the present invention provides a method for repairing lithium intercalation corrosion of a battery, the method comprising the steps of:
taking a battery subjected to lithium intercalation corrosion, wherein the battery comprises a battery cell, a packaging body and a positive electrode lug, the battery cell is sealed in the packaging body, one end of the positive electrode lug is connected with the battery cell, the other end of the positive electrode lug is positioned outside the packaging body, and the packaging body comprises a metal layer;
and connecting N resistance elements between the positive electrode lug and the metal layer, wherein N is a positive integer greater than or equal to 1, the total resistance of the N resistance elements is less than or equal to 50M omega, electrifying the battery, and completing the repair process when the insulation voltage between the positive electrode lug and the packaging body is less than 0.5V.
The implementation of the invention has at least the following advantages:
1. according to the invention, the resistance element with the total resistance of less than or equal to 50 MOmega is connected between the positive electrode lug and the metal layer, so that lithium embedding corrosion of a packaging body in the battery can be effectively prevented.
2. The invention also provides a method for repairing the battery which is corroded by lithium intercalation, for the battery which is corroded but does not leak liquid, the resistance element with the total resistance less than or equal to 50M omega is connected between the positive electrode lug and the metal layer and then electrified, so that the packaging body which is corroded by lithium intercalation can be rapidly repaired, and meanwhile, the battery is prevented from being corroded any more in the later period.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a schematic structural view of a prior art battery;
FIG. 2 is a schematic diagram of an equivalent circuit of a prior art battery;
FIG. 3 is an equivalent circuit diagram of a prior art battery in which lithium intercalation corrosion occurs;
fig. 4 is a schematic structural diagram of a battery according to an embodiment of the present invention;
fig. 5 is a schematic diagram of an equivalent circuit of a battery according to an embodiment of the invention;
fig. 6a is a test chart of the insulation voltage between the positive electrode tab and the package in a normal battery;
fig. 6b is a graph showing the insulation voltage test between the positive electrode tab and the package in the battery in which lithium intercalation corrosion has occurred;
fig. 6c is a graph illustrating the insulation voltage test between the positive electrode tab and the package body in the process of repairing the soft-package lithium ion battery with lithium intercalation corrosion according to the first embodiment;
FIG. 7a is a test chart of the corrosion days of a conventional soft-packed lithium ion battery;
fig. 7b is a test chart of the number of days of corrosion of the soft package lithium ion battery provided in example two.
Description of reference numerals:
100-electric core;
101-positive plate;
102-negative pole piece;
200-a package;
300-positive pole tab;
400-a negative electrode tab;
500-resistive element.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The battery includes a battery cell and a package body for sealing the battery cell, for example, fig. 1 is a schematic structural diagram of a battery in the prior art, as shown in fig. 1, including a battery cell 100, a package body 200, a positive tab 300 and a negative tab 400, where the battery cell 100 is used as an energy storage component of the battery, and is used for an electrochemical reaction, and generally includes a positive plate 101, a separator and a negative plate 102; the package body 200 is located outside the battery cell 100 and is used for sealing the battery cell 100, for a general battery, the package body 200 is formed by an aluminum-plastic film, the conventional aluminum-plastic film includes a heat sealing layer, a metal layer and a protective layer which are sequentially stacked, in the packaging process, two layers of aluminum-plastic films are covered on two surfaces of the battery cell 100, or the aluminum-plastic films are folded, so that the heat sealing layer in the aluminum-plastic films is located at one side close to the battery cell 100, the battery cell 100 is placed inside the two opposite layers of aluminum-plastic films, and then the opposite sides are packaged by means of heat sealing and the like, so that the opposite heat sealing layers are fused into a whole to form the package body 200; the tab is a metal conductor which is led out from the battery cell from the positive electrode and the negative electrode, so the tab is also divided into a positive tab 300 and a negative tab 400, one end of the positive tab 300 and one end of the negative tab 400 are connected with the battery cell 100, the other end of the positive tab 300 and the other end of the negative tab 400 are located outside the packaging body 200, namely, the packaging body 200 seals part of the positive tab 300 and the negative tab 400, and part of the positive tab 300 and the negative tab 400 are exposed outside the packaging body 200. It should be noted that the battery is not limited to the structure with one tab shown in fig. 1, and the two tabs or other special-shaped batteries can be protected from corrosion by using the present invention, and only a typical structure with one tab is schematically illustrated in the present invention.
For batteries, especially lithium ion batteries, lithium intercalation corrosion easily occurs in the packaging body, and then problems such as liquid leakage, gas expansion and packaging damage are caused, so that the batteries are invalid. For consumer products, although only a single battery cell is corroded, the product is usually in direct contact with personnel, such as a mobile phone, a notebook computer, a bracelet, a watch, an earphone and the like, and the battery cell corrosion, liquid leakage and flatulence bring extremely poor use experience to customers; for power products, a module of the power product is usually formed by connecting dozens of large electric cores in series-parallel connection, and the corrosion, liquid leakage and gas expansion of one electric core can cause the failure of the whole model, so that the loss is extremely high. Therefore, how to avoid lithium intercalation corrosion of the battery becomes one of the research hotspots in the field.
After repeated thinking and verification, the inventor found that the equivalent circuit diagram of the battery is shown in fig. 2, and that the insulation resistances (R in fig. 2, respectively) between the positive electrode and the package and between the negative electrode and the package of the normal battery (i.e., the battery does not suffer from lithium intercalation corrosion)1、R2Expressed) is typically several hundred M Ω to several hundred G Ω (10)8-1011Ω)，REiRepresenting the impedance of the electrolyte (the electrolyte does not conduct electrons, only conducts ions), Cpp represents the capacitance between the positive and negative electrodes and the package, which is very small and negligible, and such a high impedance corresponds to an open circuit for any circuit in the battery, and there is no leakage current (the resistor in the figure of the present invention uses gray filling to represent an open circuit, and no filling represents a via). However, when abnormal conditions occur, such as the negative electrode tab shifting during the packaging process, the negative electrode sheet piercing the heat seal layer of the package, the active material or metal particles bridging between the negative electrode sheet and the package, etc., the insulation resistance between the negative electrode and the package can be sharply reduced to several Ω to several tens of M Ω (10 Ω)1-107Ω) as the insulation resistance between them<An electronic channel can be formed when the voltage is 50M omega, in the normal use process of the battery, the packaging body, the negative plate, the electrolyte and the electronic channel form a corrosion primary battery, wherein the packaging body serves as the anode of the corrosion primary battery, the negative plate serves as the cathode, and the cathode is driven by electric field forceLi in the flake+Li is formed by the electrolyte moving to the metal layer in the package and being embedded in the lattice of aluminumxThe equivalent circuit diagram of the cell in which the Al alloy, lithium intercalation corrosion occurs, is shown in fig. 3. Because lithium intercalation corrosion is pitting corrosion, the corrosion rate is fast, and Li with extremely strong reducibility is corroded and penetrated by a packaging bodyxAl reacts with water vapor, oxygen, carbon dioxide and the like in the air to generate LiF and Li with loose and porous structures2O、Li2CO3And when water vapor in the air further enters the battery core to accelerate the gas generation of the battery core, the internal electrolyte permeates to cause the battery to swell and leak.
At present, the method for preventing lithium intercalation corrosion in the industry is single, that is, passive corrosion prevention is realized by controlling the insulation resistance between the negative electrode and the packaging body, for example, the insulation resistance between the negative electrode of the consumer electric core and the packaging body must not be less than 100M Ω, generally, the insulation resistance must be greater than 200 or 500M Ω, or the voltage between the positive electrode and the packaging body must not exceed a certain value. However, both of these monitoring methods have misjudgment and missed killing, which are determined by the capability of the testing method itself, and further improving the insulation resistance specification has little effect on corrosion prevention, and can also cause over-killing and influence the excellent rate. The inventors of the present invention have studied the mechanism of lithium intercalation corrosion of a battery thoroughly, and have proposed a battery for preventing lithium intercalation corrosion of a package, and a method of repairing a battery in which lithium intercalation corrosion has occurred, as described in detail below:
the invention provides a battery in a first aspect, which comprises a battery cell, a packaging body and a positive electrode lug, wherein the battery cell is sealed in the packaging body, one end of the positive electrode lug is connected with the battery cell, and the other end of the positive electrode lug is positioned outside the packaging body.
The packaging body comprises a metal layer, N resistance elements are connected between the positive pole lug and the metal layer, N is a positive integer greater than or equal to 1, and the total resistance of the N resistance elements is less than or equal to 50M omega.
In one embodiment, N may be 1, 2, 3, 4, 5 or other positive integer, as long as the total resistance of the N resistance elements is equal to or less than 50M Ω.
The invention provides a battery, which can effectively prevent lithium-embedded corrosion of the battery by connecting a resistance element with total resistance less than or equal to 50M omega in a positive electrode tab 300 and a metal layer, and specifically comprises the following components: according to the analysis of the mechanism of the occurrence of lithium intercalation corrosion, the necessary conditions of the occurrence of the lithium intercalation corrosion comprise a packaging body (serving as a positive electrode of a corrosion primary battery), a negative electrode (serving as a negative electrode of the corrosion primary battery), electrolyte and an electronic circuit, the method adopted by the invention is to eliminate the positive electrode in the four necessary conditions of the corrosion primary battery to inhibit corrosion, and according to the characteristics that Al element in a metal layer can be reduced but can not be oxidized (a compact oxide layer can be formed when being oxidized to prevent the reaction from going on) and Li element in the metal layer+The lithium intercalation corrosion of the metal layer cannot be prevented by the principle that the metal layer can not move from a low potential area to a high potential direction against a strong electric field, fig. 4 is a schematic diagram of a battery structure provided by an embodiment of the invention, fig. 5 is a schematic diagram of an equivalent circuit of the battery provided by the embodiment of the invention, as shown in fig. 4-5, when a resistance element 500 is connected between a positive electrode tab 300 of the battery and the metal layer in a packaging body 200, an electronic channel can be formed, namely, a positive electrode sheet 101, the packaging body 200, an electrolyte and the electronic channel can form a primary battery, the invention is named as a protection primary battery, so as to distinguish the corrosion primary battery, the positive electrode sheet has the highest potential and serves as a positive electrode of the protection primary battery, the packaging body serves as a negative electrode of the protection primary battery, the electrolyte serves as an ion channel, and the resistance element 500 serves as an electronic channel. The circuit is connected and the primary battery is discharged, and when the package body generates lithium intercalation corrosion, Li is intercalated in the metal layer+Will be removed and enter the positive plate through the electrolyte, when Li in the metal layer+After the lithium intercalation corrosion is finished, the metal aluminum cannot be oxidized, a compact oxide layer is formed on the surface of the metal aluminum to prevent the reaction from being carried out, the corrosion protection effect can be achieved, and for a battery which does not generate the lithium intercalation corrosion, the normal use of the battery cannot be influenced by the resistance element, so that the lithium intercalation corrosion can be effectively prevented by connecting the resistance element with the total resistance of less than or equal to 50M omega between the positive electrode lug and the metal layer.
It can be understood that, when the total resistance of the resistance elements is larger, the protection effect on lithium intercalation corrosion is poorer, the resistance is smaller, the protection effect is better, but there is a risk of short circuit, therefore, the total resistance of the N resistance elements is greater than or equal to 0.1 Ω, at this time, the battery cannot generate any short circuit, and no significant leakage current exists, and the battery can also play a role in protecting the packaging body from lithium intercalation corrosion.
Further, the total resistance of the N resistance elements is 1M Ω.
In one embodiment, the present invention does not further limit the arrangement of the N resistance elements, that is, the N resistance elements are connected in parallel or in series between the positive electrode tab and the metal layer, for example, two resistance elements are connected in series between the positive electrode tab and the metal layer, and the two resistance elements have respective resistance values R1And R2Total resistance R ═ R1+R2(ii) a Or two resistance elements are connected in parallel between the positive electrode lug and the metal layer, and the resistance values of the two resistance elements are R respectively1And R21/total resistance R1/R1+1/R2The total resistance R is less than or equal to 50M omega.
In a specific example, the outer surfaces of the N resistance elements are coated with adhesive paper, the adhesive paper is used for isolating the resistance elements from being in contact with external circuits, and the adhesive paper can be a material conventional in the art, for example, the adhesive paper is one or more of yellow glue, blue glue, green glue or crinkle glue.
In a specific example, the package body is formed by an aluminum plastic film, and includes a heat sealing layer, a metal layer and a protective layer, which are sequentially stacked, where the heat sealing layer is located on one side of the metal layer close to the electric core, the protective layer is located on one side of the metal layer far from the electric core, and the metal layer is located between the heat sealing layer and the protective layer.
The aluminum plastic film may be a material conventional in the art, for example, the metal layer comprises aluminum; the heat sealing layer comprises polypropylene and a compound thereof; the protective layer comprises a composite of polyamide and polyethylene terephthalate.
The cell and the tab in the battery are also performed according to the conventional technical means in the field, for example, the cell comprises a positive plate and a negative plate which are sequentially stacked, or comprises a positive plate and a negative plate which are sequentially stacked and then wound to form the battery.
Further, the positive plate comprises a positive current collector and a positive active layer arranged on at least one functional surface of the positive current collector, wherein the positive active layer comprises a positive active material, and the positive active material comprises one or more of LCO, LMO, LFP, NCM and NCA.
Further, the negative electrode sheet comprises a negative electrode current collector and a negative electrode active layer arranged on at least one functional surface of the negative electrode current collector, wherein the negative electrode active layer comprises a negative electrode active material, and the negative electrode active material comprises one or more of graphite, lithium carbonate, a silicon-oxygen compound and a silicon-carbon compound.
Further, the positive electrode tab is an aluminum foil.
Further, the negative pole tab is a copper foil.
Furthermore, the battery cell further comprises a diaphragm, and the diaphragm is positioned in front of the positive plate and the negative plate and plays a role in preventing the positive plate and the negative plate from being in contact with each other to generate short circuit.
In a second aspect, the present invention provides a method for repairing lithium intercalation corrosion of a battery, the method comprising the steps of:
taking a battery subjected to lithium intercalation corrosion, wherein the battery comprises a battery cell, a packaging body and a positive electrode lug, the battery cell is sealed in the packaging body, one end of the positive electrode lug is connected with the battery cell, the other end of the positive electrode lug is positioned outside the packaging body, and the packaging body comprises a metal layer;
and connecting N resistance elements between the positive electrode lug and the metal layer, wherein N is a positive integer greater than or equal to 1, the total resistance of the N resistance elements is less than or equal to 50M omega, electrifying the battery, and completing the repair process when the insulation voltage between the positive electrode lug and the packaging body is less than 0.5V.
The second aspect of the invention provides a repairing method, a resistance element with total resistance less than or equal to 50M omega is connected between a positive electrode lug and a metal layer to repair a battery which has undergone lithium intercalation corrosion, the structure of the battery and the connection mode of the resistance element are as described above, the insulation voltage of the battery which has undergone lithium intercalation corrosion is usually above 0.8V in the repairing process, and when the voltage is reduced and stabilized by the repairing method provided by the invention and is less than 0.5V, the corrosion repairing is finished.
The technical scheme provided by the invention is explained in detail by combining the specific embodiment as follows:
the first embodiment is as follows: this example provides a method for repairing lithium intercalation corrosion, and will prove how to repair a corroded battery to an initial state through experimental data.
Select the soft packet of lithium ion battery of a certain volume production model, because there is the metal granule in the electricity core inside, lead to negative pole and packaging body to appear the short circuit, lead to packaging body to take place to inlay lithium and corrode. The insulation voltage between the positive electrode of the normal electric core of the mass production model and the packaging body is as shown in fig. 6a, the insulation voltage is collected by a data acquisition instrument, the collection interval is 50ms, and 10s is collected totally. At the moment of starting the test, a certain current exists in the loop and is provided by a capacitor in the loop, so that the initial voltage is 1.16V, the voltage is stabilized to be 0.03V after 200ms, and the stabilized voltage is used as the insulation voltage value between the positive electrode and the packaging body. The voltage between the positive electrode of the corrosion battery and the aluminum-plastic film is stabilized at 1.84V (as shown in fig. 6 b), the voltage drop phenomenon caused by the capacitor charging in fig. 6a does not occur, and the phenomenon that the voltage is high and is kept stable can be judged as corrosion. Without any treatment, the cell will have to leak over time.
And (3) repairing the corrosion battery, connecting a resistance element with the resistance of 1 MOmega between the anode tab and the metal layer by adopting the method provided by the invention, electrifying for corrosion repair, and finishing the repair process, wherein the initial voltage is 0.65V and the voltage after the curve is stable is 0.06V as shown in figure 6 c.
For the battery core with corrosion risk, the resistance element needs to be connected to the battery all the time, if the battery core stops, the aluminum plastic film can continuously corrode under the action of a corrosion loop, and therefore the resistance element can be connected between the positive pole lug and the metal layer all the time, and lithium embedding corrosion of the battery is prevented.
Example two: this embodiment corrodes the protection through normal volume production electricity core to verify its protective effect.
30 normal soft package lithium ion batteries of certain model volume production are received, the insulation impedance between the positive electrode and the aluminum plastic film and between the negative electrode and the aluminum plastic film is more than 1G omega, the corrosion risk of the battery cell does not exist, in order to accelerate the corrosion of the battery cell, a resistance element with the resistance of 10M omega is connected between the negative electrode tab and the packaging body, and the external conduction condition (such as entering a small amount of water in a battery bin or generating metal chips to cause the formation of an electronic channel between the negative electrode and the aluminum plastic film) which possibly occurs at a client side is simulated. The set of cells was not protected and the test results are shown in fig. 7a, with 30 samples all corroded within 20 days. The fastest etch time is consistent with the theoretically calculated etch time (theoretical etch time does not take into account kinetic issues). The corrosion time was recorded using interval deletion.
And another 30 mass-production battery cores of the same model are taken, and a resistance element with the resistance of 10M omega is simultaneously connected among the positive pole lug, the negative pole lug and the aluminum plastic film metal layer, so that the conditions of accelerated corrosion and corrosion protection are simulated. As shown in fig. 7b, 30 samples did not corrode over a period of 180 days, and the potential between the package and the positive electrode of the lithium battery was measured, and no increase in the insulation voltage was observed, indicating that corrosion had not yet started. Etch time recordings were made with right deletions.
The principle is that when the conditions for forming the protective primary battery and the corrosion primary battery are met, the metal layer on the packaging body simultaneously serves as the negative electrode of the protective primary battery and the positive electrode of the corrosion primary battery, so that the metal layer only serves as a conductive channel, and Li of the negative electrode+The electrolyte is embedded into the anode, electrons of the cathode flow into the anode through the packaging body to form a complete loop, the lithium battery generates self-discharge through leakage current of the packaging body, and Li of the cathode is under the action of a strong electric field+The metal layer of the packaging body can not be embedded, and then the active anticorrosion effect on the battery is achieved.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The battery is characterized by comprising an electric core, a packaging body and a positive electrode lug, wherein the electric core is sealed in the packaging body, one end of the positive electrode lug is connected with the electric core, and the other end of the positive electrode lug is positioned outside the packaging body;
the packaging body comprises a metal layer, N resistance elements are connected between the positive pole lug and the metal layer, N is a positive integer greater than or equal to 1, and the total resistance of the N resistance elements is less than or equal to 50M omega.
2. The battery of claim 1, wherein the total resistance of the N resistive elements is equal to or greater than 0.1 Ω.
3. The battery of claim 1, wherein the total resistance of the N resistive elements is 1M Ω.
4. The battery of any of claims 1-3, wherein the N resistive elements are connected in parallel or in series between the positive tab and the metal layer.
5. The battery of any one of claims 1-4, wherein the outer surface of the N resistance elements is coated with adhesive paper, and the adhesive paper is used for isolating the resistance elements from being in contact with external lines.
6. The battery of any one of claims 1-5, wherein the package body comprises a heat-sealing layer, a metal layer and a protective layer, which are sequentially stacked, the heat-sealing layer is located on a side of the metal layer close to the battery cell, and the protective layer is located on a side of the metal layer away from the battery cell.
7. The battery of claim 6, wherein the metal layer comprises aluminum.
8. The cell defined in claim 6, wherein the heat seal layer comprises polypropylene and composites thereof.
9. The battery of claim 6, wherein the protective layer comprises a composite of polyamide and polyethylene terephthalate.
10. A method for repairing a battery from lithium intercalation corrosion, the method comprising the steps of:
taking a battery subjected to lithium intercalation corrosion, wherein the battery comprises a battery cell, a packaging body and a positive electrode lug, the battery cell is sealed in the packaging body, one end of the positive electrode lug is connected with the battery cell, the other end of the positive electrode lug is positioned outside the packaging body, and the packaging body comprises a metal layer;
and connecting N resistance elements between the positive electrode lug and the metal layer, wherein N is a positive integer greater than or equal to 1, the total resistance of the N resistance elements is less than or equal to 50M omega, electrifying the battery, and completing the repair process when the insulation voltage between the positive electrode lug and the packaging body is less than 0.5V.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111163985.6A CN113948758B (en) | 2021-09-30 | 2021-09-30 | Battery and battery repairing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111163985.6A CN113948758B (en) | 2021-09-30 | 2021-09-30 | Battery and battery repairing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113948758A true CN113948758A (en) | 2022-01-18 |
| CN113948758B CN113948758B (en) | 2023-09-26 |
Family
ID=79329687
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111163985.6A Active CN113948758B (en) | 2021-09-30 | 2021-09-30 | Battery and battery repairing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113948758B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1411577A1 (en) * | 2002-10-16 | 2004-04-21 | Renault s.a.s. | Device for diagnosing the state of corrosion of a battery, in particular one of a motor vehicle |
| JP2006128038A (en) * | 2004-11-01 | 2006-05-18 | Nissan Motor Co Ltd | Battery structure body |
| JP2007095423A (en) * | 2005-09-28 | 2007-04-12 | Dainippon Printing Co Ltd | Lithium ion battery tab, its manufacturing method, and lithium ion battery using the same |
| JP2009064767A (en) * | 2007-08-15 | 2009-03-26 | Nissan Motor Co Ltd | Battery pack |
| CN103048376A (en) * | 2011-10-14 | 2013-04-17 | 深圳市海盈科技有限公司 | Method for detecting corrosion condition inside lithium ion battery with flexible package |
| CN111007408A (en) * | 2019-12-12 | 2020-04-14 | 国联汽车动力电池研究院有限责任公司 | Soft package lithium ion battery edge voltage defect detection, analysis and repair method and device |
| CN212750950U (en) * | 2020-02-28 | 2021-03-19 | 浙江克能新能源科技有限公司 | Lithium ion battery for inhibiting aluminum plastic film corrosion of soft package battery |
| CN112751111A (en) * | 2020-12-30 | 2021-05-04 | 远景动力技术(江苏)有限公司 | Soft package lithium ion battery and application thereof |
| CN214254673U (en) * | 2021-02-05 | 2021-09-21 | 远景动力技术(江苏)有限公司 | Battery module capable of preventing electrochemical corrosion |
-
2021
- 2021-09-30 CN CN202111163985.6A patent/CN113948758B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1411577A1 (en) * | 2002-10-16 | 2004-04-21 | Renault s.a.s. | Device for diagnosing the state of corrosion of a battery, in particular one of a motor vehicle |
| JP2006128038A (en) * | 2004-11-01 | 2006-05-18 | Nissan Motor Co Ltd | Battery structure body |
| JP2007095423A (en) * | 2005-09-28 | 2007-04-12 | Dainippon Printing Co Ltd | Lithium ion battery tab, its manufacturing method, and lithium ion battery using the same |
| JP2009064767A (en) * | 2007-08-15 | 2009-03-26 | Nissan Motor Co Ltd | Battery pack |
| CN103048376A (en) * | 2011-10-14 | 2013-04-17 | 深圳市海盈科技有限公司 | Method for detecting corrosion condition inside lithium ion battery with flexible package |
| CN111007408A (en) * | 2019-12-12 | 2020-04-14 | 国联汽车动力电池研究院有限责任公司 | Soft package lithium ion battery edge voltage defect detection, analysis and repair method and device |
| CN212750950U (en) * | 2020-02-28 | 2021-03-19 | 浙江克能新能源科技有限公司 | Lithium ion battery for inhibiting aluminum plastic film corrosion of soft package battery |
| CN112751111A (en) * | 2020-12-30 | 2021-05-04 | 远景动力技术(江苏)有限公司 | Soft package lithium ion battery and application thereof |
| CN214254673U (en) * | 2021-02-05 | 2021-09-21 | 远景动力技术(江苏)有限公司 | Battery module capable of preventing electrochemical corrosion |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113948758B (en) | 2023-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP3989325A1 (en) | Lithium-ion battery and device | |
| CN108427077A (en) | A kind of experimental method for analysing lithium using reference electrode monitoring cathode | |
| US20030013007A1 (en) | Cell structure for electrochemical devices and method of making same | |
| EP2782181A1 (en) | Layer cell, assembled battery including layer cell, and method for assembling layer cell | |
| CN111009679A (en) | Three-electrode battery cell, three-electrode soft package battery and preparation method thereof | |
| CN105765766B (en) | Lithium ion secondary battery and its manufacturing method | |
| JP2008047510A (en) | Power storage device | |
| JP5583480B2 (en) | Inspection method for lithium ion secondary battery | |
| JP4060576B2 (en) | Flat battery | |
| JP2004273139A (en) | Lithium secondary battery | |
| CN108061859A (en) | A kind of method of soft-package battery reference electrode performance verification | |
| WO2022000307A1 (en) | Electrochemical apparatus and electronic apparatus including electrochemical apparatus | |
| JP2000353502A (en) | Nonaqueous electrolyte secondary battery | |
| JP2015015245A (en) | Battery having curved surface | |
| CN112103554A (en) | Three-electrode repairable lithium ion battery | |
| JP3183139B2 (en) | Short-circuit detection method for cylindrical batteries | |
| JP7372981B2 (en) | Electrochemical devices and electronic devices including electrochemical devices | |
| CN113948758A (en) | Battery and battery repairing method | |
| CN116646621A (en) | Detachable battery cell negative electrode exogenous lithium supplementing method | |
| CN110600285A (en) | Lithium separation-free pre-lithium intercalation method for cathode of lithium ion electrochemical energy storage device | |
| WO2022000329A1 (en) | Electrochemical apparatus and electronic apparatus | |
| CN108962613B (en) | Method for reducing leakage current of lithium ion capacitor | |
| WO2022051914A1 (en) | Electrochemical device and electronic device | |
| JP2008041489A (en) | Lithium ion electricity storage element | |
| CN111864277A (en) | Method for manufacturing lithium ion battery capable of resisting storage discharge to zero volt |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |