CN113823848A - Lithium ion battery - Google Patents
Lithium ion battery Download PDFInfo
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- CN113823848A CN113823848A CN202010564490.3A CN202010564490A CN113823848A CN 113823848 A CN113823848 A CN 113823848A CN 202010564490 A CN202010564490 A CN 202010564490A CN 113823848 A CN113823848 A CN 113823848A
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- lithium
- ion battery
- lithium ion
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 51
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 192
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 192
- 239000013589 supplement Substances 0.000 claims abstract description 123
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 46
- 239000000463 material Substances 0.000 claims description 29
- 239000006258 conductive agent Substances 0.000 claims description 16
- 239000011888 foil Substances 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 15
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 13
- -1 polyethylene Polymers 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 9
- 229910010177 Li2MoO3 Inorganic materials 0.000 claims description 8
- 229910009731 Li2FeSiO4 Inorganic materials 0.000 claims description 6
- 229910001216 Li2S Inorganic materials 0.000 claims description 6
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229910003349 Li2CuO2 Inorganic materials 0.000 claims description 4
- 229910008722 Li2NiO2 Inorganic materials 0.000 claims description 4
- 229910010699 Li5FeO4 Inorganic materials 0.000 claims description 4
- 229910010532 LiFeBO3 Inorganic materials 0.000 claims description 4
- IDBFBDSKYCUNPW-UHFFFAOYSA-N lithium nitride Chemical compound [Li]N([Li])[Li] IDBFBDSKYCUNPW-UHFFFAOYSA-N 0.000 claims description 4
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- 239000004800 polyvinyl chloride Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 11
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
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- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—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
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a lithium ion battery, which comprises: a metal housing; the pole core is arranged in the metal shell and comprises a positive pole piece and a negative pole piece; mend lithium utmost point piece, mend lithium utmost point piece and locate metal casing with between the utmost point core and include: a current collector; the deformation insulating layer is arranged on the surface of one side, close to the metal shell, of the current collector and isolates the metal shell from the current collector; the lithium supplement layer is arranged on the surface of one side, close to the pole core, of the current collector; and the deformation insulating layer deforms and shrinks at a preset temperature so as to expose the current collector part and be electrically conducted with the metal shell. The lithium ion battery provided by the invention has low cost, can ensure the capacity, the rate capability and the cycle performance, and can realize active control of the lithium supplement amount and the lithium supplement time.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a lithium ion battery.
Background
Compared with other chemical power supplies, the lithium ion battery has higher energy density, stronger discharge capacity, longer service life and less pollution. In the first charging process of the lithium ion battery, a solid electrolyte membrane can be formed on the surface of the negative pole piece, and a part of lithium ions transferred from the positive pole can be consumed, so that the lithium ions are lost, the capacity of the lithium ion battery is influenced, and the service life of the lithium ion battery is influenced.
For this reason, in the lithium ion battery in the related art, a lithium supplement coating is usually added outside the positive plate, or a lithium-containing additive is added in the material of the positive plate, which all change the structure of the positive plate, and the cost is increased along with the change of the process. And the lithium-containing additive and the lithium-supplementing coating do not play a role after lithium is supplemented, but still exist in the positive plate, so that the impedance of the battery is increased, and the capacity, rate capability and cycle performance of the battery are influenced. Meanwhile, the existing lithium supplementing mode cannot realize active control on the lithium supplementing quantity and the lithium supplementing time.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, an object of the present invention is to provide a lithium ion battery, which is low in cost, and can ensure capacity, rate capability and cycle performance, and can realize active control of lithium supplement amount and lithium supplement time.
To achieve the above object, an embodiment according to the present invention provides a lithium ion battery, including: a metal housing; the pole core is arranged in the metal shell and comprises a positive pole piece and a negative pole piece; mend lithium utmost point piece, mend lithium utmost point piece and locate metal casing with between the utmost point core and include: a current collector; the deformation insulating layer is arranged on the surface of one side, close to the metal shell, of the current collector and isolates the metal shell from the current collector; the lithium supplement layer is arranged on the surface of one side, close to the pole core, of the current collector; and the deformation insulating layer deforms and shrinks at a preset temperature so as to expose the current collector part and be electrically conducted with the metal shell.
According to the lithium ion battery and the lithium ion battery, the lithium supplementing pole piece is additionally arranged in the battery, and the characteristic that the deformation insulating layer in the lithium supplementing pole piece deforms and contracts at the preset temperature is utilized, so that the lithium can be supplemented when needed, in addition, the original structure of the positive pole piece is not required to be changed, the cost increase caused by the process change of the positive pole piece can be avoided, and the lithium supplementing pole piece is independently arranged, so that the impedance of the positive pole piece and the negative pole piece cannot be increased by substances remained on the pole piece after lithium is supplemented, and the influence on the performances of the battery such as multiplying power, circulation and the like can be avoided.
In addition, by controlling the self-discharge time of the lithium supplement pole piece, the active control of the lithium supplement amount and the lithium supplement time of the positive pole piece can be realized, and the lithium supplement pole piece can also exert different lithium supplement effects, so that the lithium supplement is more flexible.
In addition, the lithium supplementing pole piece and the positive pole piece are not communicated when the battery works normally, namely, the lithium supplementing can be achieved without being communicated when the active lithium is sufficient at the initial stage of the battery circulation, the lithium supplementing can be communicated when the battery capacity is attenuated after the battery is circulated for a certain time, and the lithium supplementing can also be communicated after the battery is charged for the first time, so that the lithium supplementing time is more flexible.
According to some embodiments of the invention, the predetermined temperature is a temperature higher than a temperature at which the lithium ion battery is normally used.
According to some embodiments of the invention, the shape-changing insulating layer comprises one or more of polyethylene, polypropylene, polyvinyl chloride, and polyethylene terephthalate.
According to some embodiments of the invention, the thickness of the deformable insulating layer is 1 μm to 50 μm.
According to some embodiments of the invention, the lithium supplement layer comprises a lithium supplement material comprising an inert metal lithium powder, Li2S、Li3N、Li2MoO3、LiFeBO3、Li2FeSiO4、Li5FeO4、Li2NiO2And Li2CuO2At least one of (1).
According to some specific embodiments of the present invention, the lithium supplement layer further comprises a conductive agent and a binder, and a mass ratio of the lithium supplement material, the conductive agent and the binder in the lithium supplement layer is 80% to 96%: 2% -10%: 2 to 10 percent.
According to some embodiments of the invention, the lithium supplement layer has a thickness of 10 μm to 500 μm.
According to some embodiments of the invention, the current collector is an aluminum foil, a copper foil, or a stainless steel mesh.
According to some embodiments of the invention, the deformable insulation layer is in intimate contact with the metal shell and the lithium supplement layer is in intimate contact with the pole core.
According to some specific embodiments of the present invention, the lithium supplement electrode sheet is disposed at least one end of the electrode core in an axial direction, and the lithium supplement electrode sheet is disposed perpendicular to the axial direction of the electrode core.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic structural diagram of a lithium supplement pole piece of a lithium ion battery according to an embodiment of the invention.
Reference numerals:
the lithium supplement device comprises a lithium supplement pole piece 1, a deformation insulating layer 2, a current collector 3 and a lithium supplement layer 4.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
A lithium ion battery according to an embodiment of the present invention is described below.
The lithium ion battery according to the embodiment of the invention comprises a metal shell, a pole core and a lithium supplement pole piece 1.
As shown in fig. 1, the lithium supplement pole piece 1 includes a current collector 3, a deformed insulating layer 2 and a lithium supplement layer 4.
The deformation insulating layer 2 is located a side surface of the mass flow body 3, and the lithium supplement layer 4 is located another side surface of the mass flow body 3, for example, the deformation insulating layer 2 and the lithium supplement layer 4 are respectively arranged on two sides of the thickness direction of the mass flow body 3, the deformation insulating layer 2 can be located a side surface of the mass flow body 3 close to the metal shell, and the lithium supplement layer 4 can be located a side surface of the mass flow body 3 close to the pole core.
In the lithium ion battery of the embodiment of the invention, the positive plate and the negative plate are wound or laminated to form the pole core and are arranged in the metal shell. Mend lithium pole piece 1 and locate between metal casing and the utmost point core, isolated metal casing and current collector 3 of deformation insulating layer 2. Of course, the metal shell is also filled with electrolyte to realize the ion conduction between the lithium supplement pole piece 1 and the positive pole piece.
Wherein, the deformation insulating layer 2 deforms and shrinks at a preset temperature, so that the current collector 3 is partially exposed and electrically connected with the metal shell.
Wherein the predetermined temperature may be higher than a temperature at which the battery is normally used, for example, 50 to 80 ℃.
The shape-changing insulating layer 2 comprises an insulating material which shrinks at a temperature higher than the normal use temperature of the battery, and can be selected from one or more of polyethylene, polypropylene, polyvinyl chloride and polyethylene terephthalate.
The following describes a lithium supplementing process of a lithium ion battery according to an embodiment of the present invention by way of example.
When the lithium needs to be replenished to the battery, the battery is placed in a preset temperature environment, the positive plate and the metal shell are electrically connected, the deformation insulating layer 2 deforms and shrinks at a preset temperature, so that the whole current collector 3 cannot be covered, the exposed current collector 3 is in electrical contact with the metal shell, an electronic passage between the positive plate, the lithium replenishing plate 1 and the metal shell is formed, an ion passage between the positive plate and the lithium replenishing plate 1 can be formed by electrolyte existing in the metal shell, and the discharge of the lithium replenishing plate 1 to the positive plate can be realized due to the high potential of the positive plate and the low potential of the lithium replenishing plate 1, so that lithium ions are separated from the lithium replenishing material in the lithium replenishing plate 1 and are embedded into the active material of the positive plate, the lithium replenishing of the lithium replenishing plate 1 to the positive plate is realized, and more active lithium can be provided by the positive plate for the battery circulation.
Of course, the lithium supplement pole piece 1 can also directly supplement lithium for the negative pole, and the lithium supplement can be controlled, namely, lithium is supplemented again when needed, and the lithium supplement amount is controlled by controlling the lithium supplement time. The metal shell is communicated with the negative plate, so that the lithium supplement plate 1 and the negative plate form a new positive electrode and a new negative electrode, and lithium ions are separated out through the lithium supplement plate and are embedded into the negative electrode, so that the direct lithium supplement of the negative electrode is realized.
The lithium ion battery provided by the embodiment of the invention can be used for supplementing lithium to the positive plate or the negative plate after the lithium ion battery is charged for the first time, and can also be used for supplementing lithium when the capacity of the battery is reduced after the battery is used for a period of time, namely the lithium ion battery provided by the embodiment of the invention can be used for supplementing lithium when needed, so that the lithium supplementing time is more flexible.
According to the lithium ion battery provided by the invention, the lithium supplement pole piece 1 is additionally arranged in the battery, and the characteristic that the deformation insulating layer 2 in the lithium supplement pole piece 1 deforms and shrinks at a preset temperature is utilized, so that lithium can be supplemented when needed, in addition, the effect of lithium supplement can be realized without changing the original structure of the positive pole piece, the cost increase caused by the process change of the positive pole piece is avoided, and the influence on the multiplying power performance, the cycle performance and the like of the battery, which is caused by the fact that the lithium supplement layer is directly introduced into the positive pole piece or the negative pole piece in the prior art, and the impedance of the positive pole piece or the negative pole piece is increased by substances remained in the lithium supplement layer after lithium supplement, can also be avoided.
And by controlling the lithium supplementing time, the active control of the lithium supplementing amount of the positive plate or the negative plate can be realized, so that the lithium supplementing is more flexible.
Therefore, the lithium ion battery provided by the invention is low in cost, can ensure the battery capacity, the rate capability and the cycle performance, and can realize active control of the lithium supplement amount and the lithium supplement time.
In some embodiments of the present invention, the lithium supplement electrode sheet 1 is disposed between the metal shell and the electrode core, the deformable insulation layer 2 is in close contact with the metal shell, and the lithium supplement layer 4 is in close contact with the electrode core. Thereby, the lithium supplement electrode sheet 1 can be compactly arranged in the metal case, thereby contributing to the overall miniaturization of the lithium ion battery.
Wherein, mend lithium pole piece 1 and locate the epaxial at least one end of utmost point core, mend lithium pole piece 1 perpendicular to the axial setting of utmost point core. In the assembling process, the lithium supplement pole piece 1 is placed in parallel with the end face of the pole core, and the assembled body containing the pole core and the lithium supplement pole piece 1 is packaged in a metal shell to manufacture the lithium ion battery containing the lithium supplement pole piece 1.
In some embodiments of the present invention, the core contains a positive electrode sheet and a negative electrode sheet, and at least one of the positive electrode sheet and the negative electrode sheet includes a porous foil.
For example, the positive electrode sheet is made of porous aluminum foil, and the negative electrode sheet is made of porous copper foil. The use of the porous foil can shorten the lithium ion migration path and improve the lithium supplement efficiency when the battery supplements lithium.
Here, the current collector 3 may also be made of a porous foil material, such as a porous copper foil, a porous aluminum foil, or the like.
In some embodiments of the present invention, the thickness of the deformable insulating layer 2 is 1 μm to 50 μm, for example, the thickness of the deformable insulating layer 2 is 1 μm to 10 μm. So, the thickness of deformation insulating layer 2 is thinner, and occupation space is littleer, guarantees not to occupy the space of utmost point core, and can guarantee the isolated effect to mass flow body 3 and metal casing.
In some embodiments of the present invention, the lithium supplement layer 4 includes a lithium supplement material, and may further include a conductive agent and a binder. In the prepared lithium supplement layer 4, the lithium supplement material, the conductive agent and the binder are uniformly mixed together.
Further, the lithium supplement material comprises inert metal lithium powder and Li2S、Li3N、Li2MoO3、LiFeBO3、Li2FeSiO4、Li5FeO4、Li2NiO2And Li2CuO2At least one of (1). Example (b)For example, the lithium-supplementing material is inert lithium powder or Li2S、Li2MoO3And Li2FeSiO4Because the lithium removal potential of the materials is obviously lower than that of the existing anode materials, the materials are easy to be oxidized and removed with lithium, and the products after lithium removal are stable, so that the battery system is not influenced.
In some embodiments of the present invention, in the lithium supplement layer 4, the mass ratio of the lithium supplement material, the conductive agent and the binder is 80% to 96%: 2% -10%: 2 to 10 percent.
Specifically, the lithium supplement material in the lithium supplement layer 4 is an active material of the lithium supplement electrode sheet 1, and the content of the active material determines the amount of active lithium that can be provided by the lithium supplement layer 4, so the content of the lithium supplement material cannot be too low, for example, 90% to 96%, and further 94% to 96%.
The conductive agent in the lithium supplement layer 4 plays a role in conducting electrons, and in order to ensure the conductivity of the lithium supplement layer 4, the content of the conductive agent is not lower than 2%, but not too high, which may affect the proportion of active materials and the lithium supplement amount of the lithium supplement layer 4, for example, the content of the conductive agent is 2% to 5%, and further 2% to 3%.
The binder in the lithium supplement layer 4 plays a role in binding and fixing the lithium supplement material and the conductive agent on the current collector 3, and in order to play a good binding role, the content of the binder is not lower than 2%, but the content of the binder is not too high, and the proportion of active substances and the lithium supplement amount of the lithium supplement layer 4 are influenced by the too high content of the binder. For example, the content of the binder is 2% to 5%, and more preferably 2% to 3%.
In some embodiments of the invention, the conductive agent comprises at least one of acetylene black, carbon nanotubes, graphene, conductive carbon black, and conductive graphite.
In some embodiments of the invention, the binder comprises at least one of polyvinylidene fluoride, polytetrafluoroethylene, polyacrylate, polyurethane, epoxy, styrene butadiene rubber, polymethyl cellulose, sodium polymethyl cellulose, hydroxypropyl methyl cellulose, and polypropylene glycol.
In some embodiments of the invention, the lithium supplement layer 4 has a thickness of 10 μm to 500. mu.m. For example, the thickness of the lithium supplement layer 4 is 50 μm to 200. mu.m, and further 75 μm to 150. mu.m. The smaller the thickness of the lithium supplement layer 4, the less the content of the lithium supplement substance, the less active lithium it can provide, and the larger the thickness of the lithium supplement layer 4, the more active lithium it can provide, but the more difficult it is to delithiate the lithium supplement substance at the position close to the current collector 3, so the thickness of the lithium supplement is not too small nor too large.
In some embodiments of the invention, the current collector 3 is an aluminum foil, a copper foil, or a stainless steel mesh.
Wherein, the copper foil is unstable in a high voltage section and is suitable for lithium supplement materials with lower voltage, for example, the copper foil is suitable for inert lithium powder lithium supplement materials, the aluminum foil is unstable in lower voltage and is stable in higher voltage, so that the aluminum foil is suitable for lithium supplement materials with higher voltage, for example, the aluminum foil is suitable for Li2S、Li3N、Li2MoO3、LiFeBO3、Li2FeSiO4、Li5FeO4、Li2NiO2And Li2CuO2And (5) supplementing lithium materials. For example, when the lithium supplement material is inert lithium powder, the current collector 3 is selected to be copper foil; when the lithium-supplementing material is Li2S、Li2MoO3And Li2FeSiO4In this case, the current collector 3 is selected to be an aluminum foil.
The method for coating the slurry for the lithium supplement electrode sheet 1 of the lithium ion battery according to the embodiment of the present invention is described below.
For example, adding lithium supplement material powder, a conductive agent and a binder into a dispersing agent according to a certain mass ratio, uniformly stirring to obtain lithium supplement slurry, coating the lithium supplement slurry on the surface of one side of a current collector 3, drying to obtain a pole piece containing a lithium supplement layer 4, and attaching a deformation insulating material film on the surface of the other side of the current collector 3 to obtain the lithium supplement pole piece 1 containing a deformation insulating layer 2 and the lithium supplement layer 4. The dispersant of the lithium supplement slurry may be one or more selected from the group consisting of N-methylpyrrolidone (NMP), Dimethylformamide (DMF), Diethylformamide (DEF), Dimethylsulfoxide (DMSO), and Tetrahydrofuran (THF).
The advantages of the lithium ion battery according to the embodiment of the present invention over the existing lithium ion battery are illustrated by specific experiments as follows.
Example 1
With Li2MoO3Uniformly mixing acetylene black and polyvinylidene fluoride (PVDF) as conductive agents and N-methyl pyrrolidone (NMP) as dispersing agents according to the mass ratio of the acetylene black to the NMP of 95:3:2:50, then coating the mixture on an aluminum foil, and then placing the aluminum foil in an oven at 80 ℃ for vacuum drying for 24 hours to obtain the pole piece with the lithium supplement layer 4. And tightly attaching the polyethylene film to one side of the blank of the pole piece, tabletting and rolling to prepare the lithium supplement pole piece 1, wherein the thickness of the deformed insulating layer 2 is 1 micron, and the thickness of the lithium supplement layer 4 is 150 microns. The two lithium supplement pole pieces 1 are respectively arranged on the upper side and the lower side of a pole core (anode NCM622 ternary material, cathode graphite), the lithium supplement layer 4 is contacted with the pole core, a new pole core is arranged in a square metal shell, and the novel lithium ion battery S1 is packaged.
Example 2
Taking inert lithium powder as a lithium supplement material, acetylene black as a conductive agent, polyvinylidene fluoride (PVDF) as a binder and N-methyl pyrrolidone (NMP) as a dispersing agent, uniformly mixing the inert lithium powder, the acetylene black, the PVDF and the NMP in a mass ratio of 96:2:2:50, coating the mixture on a copper foil, and then placing the copper foil in an oven at 80 ℃ for vacuum drying for 24 hours to prepare the pole piece with the lithium supplement layer 4. And tightly attaching the polyethylene film to one side of the blank of the pole piece, tabletting and rolling to prepare the lithium supplement pole piece 1, wherein the thickness of the deformed insulating layer 2 is 10 microns, and the thickness of the lithium supplement layer 4 is 75 microns. The two lithium supplement pole pieces 1 are respectively arranged on the upper side and the lower side of a pole core (anode NCM622 ternary material, cathode graphite), the lithium supplement layer 4 is contacted with the pole core, a new pole core is arranged in a square metal shell, and the novel lithium ion battery S2 is packaged.
Example 3
With Li2MoO3Uniformly mixing acetylene black and polyvinylidene fluoride (PVDF) as conductive agents and N-methyl pyrrolidone (NMP) as dispersing agents according to the mass ratio of the acetylene black to the NMP to 94:3:3:50, then coating the mixture on an aluminum foil, and then placing the aluminum foil in an oven at 80 ℃ for vacuum drying for 24 hours to obtain the pole piece with the lithium supplement layer 4. Closely attaching polyethylene film to one side of the blank of the pole piece, tabletting, and rolling to obtain a lithium-supplementing pole piece 1 with a deformed insulating layer 2 of 5 μm thicknessThe lithium layer 4 has a thickness of 150 μm. The two lithium supplement pole pieces 1 are respectively arranged on the upper side and the lower side of a pole core (anode NCM622 ternary material, cathode graphite), the lithium supplement layer 4 is contacted with the pole core, a new pole core is arranged in a square metal shell, and the novel lithium ion battery S3 is packaged.
Comparative example 1
Referring to the method of example 1, a battery sample DS10 was prepared, except that the core used was a conventional core, and no lithium supplement tab was included.
Further experimental tests were carried out by the above lithium ion batteries S1, S2, S3 and DS10, and the test methods and results of the above experiments are as follows.
(1) And (3) charging test:
the charging test is carried out on a charging and discharging tester, the batteries S1, S2, S3 and DS10 are charged to 4.3V at a rate of 0.1C at 25 ℃, the charging capacity is tested to obtain the charging capacity a, after standing for 5min, the positive pole is in short circuit with the metal shell, the batteries are placed in a 60 ℃ oven to keep the short circuit state for 24h, then the short circuit is disconnected, the batteries are charged to 4.3V at a rate of 0.1C, and the charging capacity is tested to obtain the charging capacity b. The test results are shown in Table 1.
TABLE 1
| Battery numbering | Charging Capacity a (Ah) | Charging Capacity b (Ah) |
| S1 | 104.83 | 2.55 |
| S2 | 104.62 | 2.62 |
| S3 | 104.77 | 2.51 |
| DS10 | 104.45 | 0.05 |
The test result shows that the charging capacity of the DS10 battery without the lithium supplementing positive plate is extremely small, only 0.05Ah, while the charging capacities b of the S1, S2 and S3 batteries with the second lithium supplementing positive plate respectively reach 2.55Ah, 2.62Ah and 2.51Ah, which indicates that the lithium supplementing plate 1 supplements lithium to the positive plates of the S1, S2 and S3 batteries, so that the positive plates can be continuously delithiated to the negative electrode.
(2) And (3) cycle testing:
the cycle test was carried out on a charge/discharge tester, in which the batteries S1, S2, S3 and DS10 were loaded and subjected to 300 cycles at 25 ℃ under a current of 0.5C, an upper limit voltage of 4.3V and a lower limit voltage of 3V. And after circulation is finished, charging the battery to 4.3V at a multiplying power of 0.5C, testing the charging capacity to obtain the charging capacity 301-1, standing for 5min, short-circuiting the positive pole and the metal shell, putting the battery into a 60 ℃ oven, keeping the short-circuited state for 24h, disconnecting the short circuit, charging to 4.3V at a multiplying power of 0.5C, testing the charging capacity to obtain the charging capacity 301-2. The test results are shown in Table 2.
TABLE 2
| Battery numbering | Charging capacity 301-1(Ah) | Charging capacity 301-2(Ah) |
| S1 | 97.95 | 2.53 |
| S2 | 97.84 | 2.56 |
| S3 | 97.89 | 2.48 |
| DS10 | 97.51 | 0.04 |
The test result shows that the lithium supplementing pole piece 1 can still supplement lithium for the positive pole even after 300 cycles of the battery, which indicates that the lithium supplementing pole piece 1 is stable in the battery, and the lithium supplementing pole piece 1 can play a lithium supplementing role only by short-circuiting the positive pole column and the metal shell and placing the battery in an oven at the temperature exceeding the deformation transition temperature of the deformation insulating layer 2.
Other configurations and operations of lithium ion batteries according to embodiments of the present invention are known to those of ordinary skill in the art and will not be described in detail herein.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
In the description herein, references to the description of "a particular embodiment," "a particular example," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (10)
1. A lithium ion battery, comprising:
a metal housing;
the pole core is arranged in the metal shell and comprises a positive pole piece and a negative pole piece;
mend lithium utmost point piece, mend lithium utmost point piece and locate metal casing with between the utmost point core and include:
a current collector;
the deformation insulating layer is arranged on the surface of one side, close to the metal shell, of the current collector and isolates the metal shell from the current collector;
the lithium supplement layer is arranged on the surface of one side, close to the pole core, of the current collector;
and the deformation insulating layer deforms and shrinks at a preset temperature so as to expose the current collector part and be electrically conducted with the metal shell.
2. The lithium ion battery of claim 1, wherein the predetermined temperature is a temperature higher than a temperature at which the lithium ion battery is normally used.
3. The lithium ion battery of claim 1, wherein the shape changing insulating layer comprises one or more of polyethylene, polypropylene, polyvinyl chloride, and polyethylene terephthalate.
4. The lithium ion battery of claim 1, wherein the deformed insulating layer has a thickness of 1 μm to 50 μm.
5. The lithium ion battery of claim 1, wherein the lithium supplement layer comprises a lithium supplement material selected from the group consisting of inert metal lithium powder, Li2S、Li3N、Li2MoO3、LiFeBO3、Li2FeSiO4、Li5FeO4、Li2NiO2And Li2CuO2At least one of (1).
6. The lithium ion battery of claim 5, wherein the lithium supplement layer further comprises a conductive agent and a binder, and the mass ratio of the lithium supplement material, the conductive agent and the binder in the lithium supplement layer is 80-96%: 2% -10%: 2 to 10 percent.
7. The lithium ion battery of claim 1, wherein the lithium supplement layer has a thickness of 10 μm to 500 μm.
8. The lithium ion battery of claim 1, wherein the current collector is an aluminum foil, a copper foil, or a stainless steel mesh.
9. The lithium ion battery of any of claims 1-8, wherein the deforming insulating layer is in intimate contact with the metal casing and the lithium supplement layer is in intimate contact with the pole core.
10. The lithium ion battery according to any one of claims 1 to 9, wherein the lithium supplement electrode sheet is provided at least one end of the electrode core in the axial direction, and the lithium supplement electrode sheet is arranged perpendicular to the axial direction of the electrode core.
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