CN114284463A - Composite lithium supplementing sheet, and battery cell and battery with same - Google Patents
Composite lithium supplementing sheet, and battery cell and battery with same Download PDFInfo
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- CN114284463A CN114284463A CN202011030722.3A CN202011030722A CN114284463A CN 114284463 A CN114284463 A CN 114284463A CN 202011030722 A CN202011030722 A CN 202011030722A CN 114284463 A CN114284463 A CN 114284463A
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- lithium
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- metal body
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 521
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 521
- 239000002131 composite material Substances 0.000 title claims abstract description 141
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 120
- 239000012528 membrane Substances 0.000 claims abstract description 249
- 229910052751 metal Inorganic materials 0.000 claims abstract description 192
- 239000002184 metal Substances 0.000 claims abstract description 192
- 239000013589 supplement Substances 0.000 claims abstract description 173
- 239000000758 substrate Substances 0.000 claims description 48
- -1 polyethylene Polymers 0.000 claims description 47
- 229920000642 polymer Polymers 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 15
- 239000004743 Polypropylene Substances 0.000 claims description 11
- 239000004020 conductor Substances 0.000 claims description 11
- 229920001155 polypropylene Polymers 0.000 claims description 11
- 239000011148 porous material Substances 0.000 claims description 11
- 239000004698 Polyethylene Substances 0.000 claims description 9
- 238000002955 isolation Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 229920000573 polyethylene Polymers 0.000 claims description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 7
- 239000007769 metal material Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000128 polypyrrole Polymers 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 33
- 230000008569 process Effects 0.000 abstract description 29
- 230000007774 longterm Effects 0.000 abstract description 10
- 238000003487 electrochemical reaction Methods 0.000 abstract description 3
- 239000007784 solid electrolyte Substances 0.000 abstract description 3
- 230000016507 interphase Effects 0.000 abstract description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 230000000295 complement effect Effects 0.000 description 4
- 238000005755 formation reaction Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 230000009469 supplementation Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000149 penetrating effect Effects 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
-
- 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
Abstract
The invention provides a composite lithium supplementing sheet which comprises a first membrane, a second membrane and at least one lithium-containing metal body. The two sides of the middle lithium-containing metal body are provided with a first membrane and a second membrane, and the outer sides of the first membrane and the second membrane can also be provided with other lithium-containing metal bodies. The part of the lithium-containing metal body which is not covered by the first membrane and the second membrane forms a first-effect lithium supplementing area for rapidly supplementing active lithium consumed by an SEI (solid electrolyte interphase) film formed in the first charge and discharge process of the battery; the part of the lithium-containing metal body covered by the first membrane and the second membrane forms a slow-release lithium supplementing area which is used for persistently supplementing active lithium lost by the battery in the long-term electrochemical reaction process. The composite lithium supplement sheet can simultaneously realize the first-effect lithium supplement and the long-term lithium supplement of the battery, can control the lithium supplement amount in the first-effect lithium supplement process and control the lithium supplement amount of the battery in the long-term use process, not only ensures the sufficient active lithium supplement of the battery, but also avoids the potential safety hazard caused by excessive lithium supplement.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a composite lithium supplement sheet, and a battery core and a battery with the composite lithium supplement sheet.
Background
The lithium ion battery has the characteristics of high energy density and high multiplying power, and the wide application of the lithium ion battery in the fields of automobiles, energy sources and the like in recent years further promotes the high requirements on the electrochemical performance of the lithium ion battery, including high energy density, high safety and long calendar service life. The electrochemical performance of the lithium ion battery is closely related to the first coulombic efficiency and the formation of a negative Solid Electrolyte Interface (SEI) film, in the first charging process of the formation of the lithium ion battery, the SEI film formed on the surface of a negative electrode can consume part of active lithium to cause the lithium loss of a positive electrode material, a common graphite negative electrode can consume about 10% of a lithium source in the first charging process, and the higher the specific capacity of the negative electrode material is, such as silicon, amorphous carbon and the like, the more the negative electrode lithium source is consumed; in addition, in addition to the first charge and discharge process, active lithium is continuously consumed during the continuous operation of the battery, causing capacity fading after cycling.
The lithium supplement of the anode or the cathode is an effective method for improving the energy density and the cycle performance of the lithium ion battery, and how to improve the first effect and continuously supplement the consumption of active lithium in the battery cycle process is a key point in the research of lithium supplement technology of the lithium ion battery. It has been studied to compensate the capacity loss of lithium ion battery during the first charge and discharge by introducing metal lithium (powder) or metal lithium salt with higher activity, but this method can only compensate the loss of battery during the first charge, and the improvement effect on the cycle life after many cycles is limited. In addition, the first lithium supplement of the battery and the continuous lithium supplement in the operation process are realized by introducing the third electrode, but the introduction of the third electrode needs to redesign the structure of the battery cell and the structure of the battery case cover, and a series of process changes and the like are caused.
Disclosure of Invention
In view of the above problems, the present invention provides a composite lithium supplement sheet, which includes a first membrane, a second membrane and at least one lithium-containing metal body. The two sides of the middle lithium-containing metal body are provided with a first membrane and a second membrane, and the outer sides of the first membrane and the second membrane can also be provided with other lithium-containing metal bodies. The part of the lithium-containing metal body which is not covered by the first membrane and the second membrane forms a first-effect lithium supplementing area for rapidly supplementing active lithium consumed by an SEI (solid electrolyte interphase) film formed in the first charge and discharge process of the battery; the part of the lithium-containing metal body covered by the first membrane and the second membrane forms a slow-release lithium supplementing area which is used for persistently supplementing active lithium lost by the battery in the long-term electrochemical reaction process. The composite lithium supplement sheet can simultaneously realize the first-effect lithium supplement and the long-term lithium supplement of the battery, can control the lithium supplement amount in the first-effect lithium supplement process and control the lithium supplement amount of the battery in the long-term use process, not only ensures the sufficient active lithium supplement of the battery, but also avoids the potential safety hazard caused by excessive lithium supplement.
The technical scheme provided by the invention is as follows:
the invention provides a composite lithium supplement sheet which comprises a first membrane, a second membrane and a first lithium-containing metal body, wherein the first membrane and the second membrane are symmetrical in structure, the first membrane and the second membrane are arranged on two sides of the first lithium-containing metal body, the first membrane and the second membrane form a slow-release lithium supplement area of the composite lithium supplement sheet from an area where the two sides cover the first lithium-containing metal body, the first membrane and the second membrane do not form a first-effect lithium supplement area of the composite lithium supplement sheet from an area where the two sides cover the first lithium-containing metal body, the first membrane and the second membrane are provided with micropores, the aperture of each micropore is 0.01-2000 mu m, the aperture ratio of each micropore to each other is 10-90%, and the area ratio of the first-effect lithium supplement area to the slow-release lithium supplement area is 1/2-1/5; or the composite lithium supplement sheet comprises a first membrane and a second membrane, the first membrane and the second membrane are arranged on two sides of the first lithium-containing metal body, the second lithium-containing metal body is arranged on the outer sides of the first membrane and the second membrane, the first membrane and the second membrane form a slow-release lithium supplement area of the composite lithium supplement sheet from an area where the first lithium-containing metal body is covered on two sides, a first-effect lithium supplement area of the composite lithium supplement sheet is formed in an area where the first lithium-containing metal body is not covered on two sides by the first membrane and the second membrane, the first membrane and the second membrane are provided with micropores, the aperture of each micropore is 0.01-2000 mu m, the porosity of each micropore is 10-90%, and the area ratio of the first-effect lithium supplement area to the slow-release lithium supplement area is 1/2-1/5.
The material of the lithium-containing metal body may be metallic lithium or a lithium-rich alloy, and the lithium-containing metal body is preferably a sheet. In the case where only the first lithium-containing metal body is provided, the first film and the second film sandwich the first lithium-containing metal body, a part of the first lithium-containing metal body is covered from both sides by the first film and the second film, and the remaining part of the first lithium-containing metal body is not covered from both sides by the first film and the second film. In the case where the first lithium-containing metal body and the second lithium-containing metal body are provided at the same time, the first lithium-containing metal body is sandwiched between the first membrane and the second membrane, the first lithium-containing metal body may be completely or partially covered by the first membrane and the second membrane, the second lithium-containing metal body is provided on the other sides of the first membrane and the second membrane opposite to the side immediately adjacent to the first lithium-containing metal body, respectively, and the second lithium-containing metal body is not covered by the first membrane and the second membrane. The lithium-containing metal body not covered with the film can be rapidly inserted or deposited on the electrode active material, thereby playing a role in first-effect lithium supplement of the battery in the formation of the battery and the previous several lithium supplement charging and discharging processes. After the part of the lithium-containing metal body which is not covered by the membrane completely reacts, and after the lithium-containing metal body covered by the membrane loses electrons, lithium ions need to be slowly released through the micropores of the membrane and are continuously embedded or deposited on the electrode active material in the whole life cycle of the battery, so that the effect of long-term lithium supplement in the whole life cycle of the battery is achieved. The area and ratio of the first-effect lithium supplementing area not covered by the membrane to the slow-release lithium supplementing area covered by the membrane can be determined according to the first-effect lithium supplementing amount and the lithium supplementing amount of the lithium supplementing in the whole life cycle.
The first lithium-containing metal body may be a monolithic structure, i.e. the first lithium-containing metal body may be a complete sheet. When the whole first lithium-containing metal body can cause the amount of the lithium supplement to exceed the required amount, the first lithium-containing metal body can also be in a structure of a plurality of separation sheets, and the separation sheets are partially connected or spaced from each other. The lithium-containing metal body with a plurality of separation sheet structures arranged in the middle of the composite lithium supplementing sheet is generally called as a first lithium-containing metal body. When the plurality of separation sheets are spaced apart from each other, it is preferable that the respective separation sheets are connected by a connection portion or connected by a substrate to form an integral structure, thereby making it easier to perform a process of preparing the composite lithium supplement sheet using the first lithium-containing metal body.
In order to partially expose the first lithium-containing metal body, the first and second membranes may be smaller in size than the first lithium-containing metal body. Alternatively, openings may be provided in the first and second diaphragms. In particular, a single opening may be provided on the first and second membranes, which may be curved, such as S-shaped, Z-shaped, or spiral shaped. Preferably, the openings are distributed uniformly over the first and second membrane, i.e. the curved shape of the openings is substantially uniformly distributed over the membrane. Alternatively, a plurality of openings may be provided on the first diaphragm and the second diaphragm, and the shape of the openings may be circular, oval, curved, polygonal, or the like. Preferably, the plurality of openings are evenly distributed over the first and second sheets, that is, the plurality of openings are approximately evenly distributed at the corners and the center area of the sheets with approximately the same spacing between the openings. The openings are uniformly distributed on the diaphragm, so that active lithium deposited or embedded in the pole piece is uniformly distributed, uniform lithium supplement of the whole pole piece is ensured, and potential safety hazards such as piercing a diaphragm by lithium dendrites caused by local excessive lithium supplement are avoided.
The composite lithium supplement sheet may further include a first substrate to which the first lithium-containing metal body may be fixedly attached. In the case where the first lithium-containing metal body is a thin foil or a structure of a plurality of separate pieces, it is preferable that the first lithium-containing metal body is fixedly attached to the first substrate in a manner such as press-fitting or bonding, whereby problems such as difficulty in processing and assembling due to curling of the foil or scattering of the separate pieces can be avoided. The first substrate may be provided with a through hole, or both sides of the first substrate may be provided with first lithium-containing metal bodies, respectively, so that the electrode active materials on both sides of the composite lithium replenishing sheet may be simultaneously replenished with lithium. The material of the first substrate may be a material that is structurally stable in the electrolyte. The first substrate may be non-conductive, for example, the material of the first substrate may be polyethylene, polypropylene, polyethylene-propylene copolymer, polytetrafluoroethylene, polyethylene terephthalate, or other polymers. Alternatively, the first substrate may be conductive, for example, the material of the first substrate may be a composite or mixture of a polymer and a conductive material, wherein the polymer may be polyethylene, polypropylene, polyethylene-propylene copolymer, polytetrafluoroethylene, polyethylene terephthalate, polypyrrole, or the like, which is electrochemically stable in an electrolyte, and the conductive material may be carbon black, carbon nanotubes, graphene, conductive metal powder, or the like; alternatively, the first substrate may be a conductive material such as copper, aluminum, etc., which may serve to both sink and conduct current.
In addition to the laminated structure composed of the first lithium-containing metal body and the diaphragms on both sides, a second lithium-containing metal body may be provided outside the diaphragms. When the second lithium-containing metal body is arranged, the first lithium-containing metal body can be completely covered by the membrane, and only the second lithium-containing metal body is used as a first-effect lithium supplementing area; alternatively, the first lithium-containing metal body may be partially covered with the film sheet, and a portion of the first lithium-containing metal body not covered with the film sheet and the second lithium-containing metal body may collectively serve as a primary lithium supplement region. The second lithium-containing metal body may be a monolithic structure, and a through hole may be provided on the second lithium-containing metal body, the through hole may be a curved shape such as an S-shape, a zigzag shape, or a spiral shape, and the through holes are uniformly arranged on the second lithium-containing metal body; alternatively, the second lithium-containing metal body may be provided with a plurality of through holes, the through holes may be circular, elliptical, curved, or polygonal, and the like, and the plurality of through holes may be uniformly distributed on the second lithium-containing metal body. The lithium supplement amount can be controlled by setting the size of the through hole, so that the condition of excessive lithium supplement is avoided; through evenly arranging the through holes, the lithium can be uniformly supplemented to the whole pole piece, and the condition of locally and excessively supplementing lithium is avoided. The second lithium-containing metal body may also be a structure of a plurality of separation sheets, which are partially connected or spaced apart from each other. The lithium supplementing quantity can be controlled by setting the size of the separating sheet, and the purpose of uniformly supplementing lithium can be achieved by uniformly arranging the separating sheet. The second lithium-containing metal body may have a uniformly distributed elongated structure such as a curved shape, and the curved shape may be, for example, an S-shape, a zigzag shape, a spiral shape, or the like.
The composite lithium supplement sheet may further include a second substrate to which the second lithium-containing metal body is fixedly attached. In the case where the second lithium-containing metal body is a thin foil, a structure of a plurality of separate pieces, or a long structure, it is preferable that the second lithium-containing metal body is fixedly attached to the second substrate by, for example, press-fitting or bonding, whereby problems such as difficulty in processing and assembling due to curling of the foil, the long structure, or scattering of the separate pieces can be avoided. The second substrate has a porous structure so that the active lithium of the first lithium-containing metal body can smoothly diffuse out through the membrane and the second substrate. The material of the second substrate may be a material which is structurally stable in the electrolyte, and may be electrically conductive or non-conductive, and may be a polymer such as polyethylene, polypropylene, polyethylene-propylene copolymer, polytetrafluoroethylene, polyethylene terephthalate, or a composite or mixture of a polymer and an electrically conductive material, where the polymer may be a polymer electrochemically stable in the electrolyte, such as polyethylene, polypropylene, polyethylene-propylene copolymer, polytetrafluoroethylene, polyethylene terephthalate, polypyrrole, or the like, and the electrically conductive material may be carbon black, carbon nanotubes, graphene, electrically conductive metal powder, or the like. When the second substrate is a conductive material such as copper, aluminum, etc., the substrate can function to both sink and conduct current. When the second lithium-containing metal body is a foil, a strip structure or a separate sheet structure, the second lithium-containing metal body can also be directly and fixedly connected to the first membrane and the second membrane, so that the first membrane and the second membrane play a role in fixedly connecting the second substrate.
The first and second membranes may be polymer conductive layers, the material of which may be a composite or mixture of polymer and conductive material, wherein the polymer can be polyethylene, polypropylene, polyethylene-propylene copolymer, polytetrafluoroethylene, polyethylene terephthalate, polypyrrole and other electrochemically stable polymers in the electrolyte, preferably gel polymer materials, such as polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polymethyl methacrylate, polyethylene oxide, aliphatic polycarbonate, polysiloxane, or the like, the conductive material may be a conductive carbon material or a conductive metal material, such as conductive carbon black, graphene, carbon nanotube, aluminum powder, copper powder, or the like, the conductivity of the first membrane and the second membrane can be controlled to be 0-5000S/cm through the doping proportion of the conductive filler. Because the conductivity of the metal lithium is very good, after the area which is not covered by the membrane is directly connected with the electrode, the metal lithium can quickly take part in reaction when the battery is charged and discharged, and the lithium loss caused by SEI film generation or side reaction can be supplemented, after the reaction of the area which is not covered by the membrane is finished, the area which is covered by the first membrane and the second membrane is electrically connected with the electrode through the first membrane and the second membrane, and the reaction of the metal lithium can be controlled by controlling the conductivity of the first membrane and the second membrane, so that the reaction of the metal lithium can be slowly supplemented with the active lithium lost by the battery reaction. The first membrane and the second membrane can also be insulating layers, the material of the insulating layers can be a polymer material which is non-conductive and electrochemically stable in the electrolyte or can be a composite of a polymer and an inorganic non-metallic material, the polymer can be polyethylene, polypropylene, polyethylene-propylene copolymer or polytetrafluoroethylene, and the like, and the inorganic non-metallic material can be alumina, silicon dioxide, and the like. The composite lithium supplementing sheet can further comprise a conductive part, the conductive part can be a conductive wire, a conductive sheet and the like, and the conductive part can be in conductive connection with the slow-release lithium supplementing area of the first lithium-containing metal body in a welding, bonding, mechanical crimping and other modes. Under the condition that the first diaphragm and the second diaphragm are insulating layers, the conductive part is used for conductively connecting the slow-release lithium supplementing region of the composite lithium supplementing sheet with a positive electrode lug of a battery or a negative electrode lug of the battery, and after the reaction of the region of the metal lithium which is not covered by the diaphragm is completed, the region covered by the diaphragm can slowly release lithium ions through micropores of the diaphragm, so that the metal lithium is controlled to play a role of continuously supplementing lithium; if the first membrane, the second membrane or the first substrate which is in contact with the first lithium-containing metal body is made of a conductive material, the conductive part can be in conductive connection with the positive electrode tab or the negative electrode tab, or the conductive part can be in conductive connection with only the first membrane, the second membrane or the first substrate. In the battery provided with the third electrode, the conductive portion may be led out and connected to the third electrode of the battery.
The invention also provides a battery cell of the battery, which comprises a positive plate, a negative plate, an isolation layer and the composite lithium supplement plate. The positive plate and the negative plate are stacked in a crossed manner, the isolation layer is arranged between the positive plate and the negative plate, and the composite lithium supplement plate is arranged inside the positive plate or between the positive plate and the isolation layer; or the composite lithium supplementing sheet is arranged inside the negative plate or between the negative plate and the isolating layer. The composite lithium supplement sheet can be arranged in each positive plate or each negative plate. In the case where the positive electrode tab and the negative electrode tab are porous electrode tabs, the composite lithium supplement tab may be disposed in two positive electrode tabs with other positive electrode tabs interposed therebetween or in two negative electrode tabs with other negative electrode tabs interposed therebetween. And lithium is supplemented to all electrode plates by active lithium diffusion in the porous electrode battery.
Preferably, the positions of the slow-release lithium supplement areas of the two adjacent composite lithium supplement tablets are staggered with each other. Therefore, the lithium can be uniformly supplemented in the whole electrode plate area in the long-term lithium supplementing process. More preferably, the positions of the slow-release lithium supplement regions of two adjacent composite lithium supplement tablets are complementary. Specifically, under the condition that the slow-release lithium supplementing region does not cover the whole electrode plate, the slow-release lithium supplementing regions of two adjacent composite lithium supplementing sheets can adopt a complementary form, the slow-release lithium supplementing region of one composite lithium supplementing sheet corresponds to the non-slow-release lithium supplementing region of the other composite lithium supplementing sheet, and the non-slow-release lithium supplementing region of one composite lithium supplementing sheet corresponds to the slow-release lithium supplementing region of the other composite lithium supplementing sheet, so that the comprehensive and uniform lithium supplementing of the whole electrode plate region can be ensured in the long-term lithium supplementing process.
Preferably, the first-effect lithium supplement regions of two adjacent composite lithium supplement sheets are staggered with each other. Therefore, the uniform lithium supplement of the whole electrode plate area in the first-effect lithium supplement process can be ensured. More preferably, the first-effect lithium supplement regions of two adjacent composite lithium supplement sheets are complementary in position. Specifically, under the condition that the first-effect lithium supplementing area does not cover the whole electrode plate, the first-effect lithium supplementing areas of two adjacent composite lithium supplementing sheets can adopt a complementary form, the first-effect lithium supplementing area of one composite lithium supplementing sheet corresponds to the non-first-effect lithium supplementing area of the other composite lithium supplementing sheet, and the non-first-effect lithium supplementing area of one composite lithium supplementing sheet corresponds to the first-effect lithium supplementing area of the other composite lithium supplementing sheet, so that the comprehensive and uniform lithium supplementing of the whole electrode plate area can be ensured in the first lithium supplementing process.
According to the invention, the battery comprises a shell and the battery core, wherein the battery core is provided with the composite lithium supplementing sheet. And in the process of preparing the battery cell, the composite lithium supplement sheet is placed into the electrode plate or is close to the electrode plate. And (4) accommodating the prepared battery cell into the shell, injecting electrolyte, and carrying out formation reaction. Since a side reaction such as an SEI film is generated at a negative electrode during the first charge and discharge of a battery, a part of active lithium is consumed. The active lithium in the first-effect lithium supplementing area of the composite lithium supplementing sheet can be rapidly deposited on or embedded into the electrode active material of the electrode plate, so that the active lithium lost during first charging is supplemented, and the first-effect lithium supplementing is rapidly realized. Active lithium is continuously lost due to side reaction and the like in the process of electrochemical reaction of the battery, and the active lithium in the slow-release lithium supplementing region of the composite lithium supplementing sheet is slowly released through the micropores of the membrane and is continuously deposited on or embedded into the electrode active material of the electrode plate, so that long-time active lithium supplementation can be realized. The battery can realize the first-effect lithium supplement and the continuous lithium supplement in the whole life cycle.
In the present invention, words of upper, lower, left, right, etc. indicating orientations are used only for clarity of presentation and do not serve any limiting purpose.
The invention has the advantages that:
1) the lithium supplement sheet structure has a dual-functional lithium supplement area, the micro-porous membrane layer is arranged on the surface of a lithium-containing metal body, the conductivity, micro-pore parameters and the through hole area of the membrane are controlled, the slow release of lithium ions is realized, the supplementary active lithium can be slowly released in the subsequent operation besides the first effect of the battery, the lithium supplement of the whole life cycle of the battery is realized, and the cycle performance of the battery is effectively improved;
2) through the design of the position and the structure of the lithium-containing metal body in the single composite lithium supplementing sheet and the adjacent composite lithium supplementing sheets, the lithium ions are uniformly embedded into the porous electrode, and then the uniform lithium supplementation of the whole battery is realized.
Drawings
Fig. 1(a) and 1(b) are an exploded view and an assembled view of a composite lithium supplement sheet according to a first embodiment of the present invention;
fig. 2(a) and 2(b) are an exploded view and an assembled view of a composite lithium supplement sheet according to a second embodiment of the present invention;
fig. 3(a) and 3(b) are an exploded view and an assembled view of a composite lithium supplement sheet according to a third embodiment of the present invention;
fig. 4(a) and 4(b) are an exploded view and an assembled view of a composite lithium supplement sheet according to a fourth embodiment of the present invention;
fig. 5(a) and 5(b) are an exploded view and an assembled view of a composite lithium supplement sheet according to a fifth embodiment of the present invention;
fig. 6(a) and 6(b) are an exploded view and an assembled view of a composite lithium supplement sheet according to a sixth embodiment of the present invention;
fig. 7(a) and 7(b) are an exploded view and an assembled view of a composite lithium supplement sheet according to a seventh embodiment of the present invention;
fig. 8(a) and 8(b) are an exploded view and an assembled view of a composite lithium supplement sheet according to an eighth embodiment of the present invention;
fig. 9 is a partially exploded schematic view of a battery cell according to a first embodiment of the present invention;
fig. 10 is a partially exploded view of a battery cell according to a second embodiment of the present invention.
List of reference numerals
H. H1, H2-sustained release lithium supplementing zone
S, S1, S2-first effect lithium supplement region
1. 1a, 1 b-first lithium-containing metal body
2. 2a, 2 b-first diaphragm
3. 3a, 3 b-second diaphragm
4. 4a, 4 b-first substrate
5-conductive part
6-opening
7-second lithium-containing Metal body
8-through hole
9-second substrate
10-positive plate
11-negative plate
12-barrier layer
13 a-first composite lithium supplement sheet
13 b-second composite lithium supplement sheet
Detailed Description
The invention will be further explained by embodiments in conjunction with the drawings.
Fig. 1(a) and 1(b) are an exploded view and an assembled view of a composite lithium supplement sheet according to a first embodiment of the present invention. In the embodiment shown in fig. 1(a) and 1(b), the composite lithium supplement sheet includes a first lithium-containing metal body 1, a first membrane sheet 2, and a second membrane sheet 3. The first lithium-containing metal body 1 is a monolithic structure. The first membrane 2 and the second membrane 3 are made of a composite of polyethylene and conductive carbon black, and the first membrane 2 and the second membrane 3 are provided with micropores, the pore diameter of each micropore is 1 mu m, and the porosity of each through hole is 30%. The first diaphragm 2 and the second diaphragm 3 are respectively positioned at two sides of the first lithium-containing metal body 1, and when the first diaphragm 2 and the second diaphragm 3 are fixedly connected to the first lithium-containing metal body 1, a part of the upper side of the first lithium-containing metal body 1 is not covered. The middle-lower part of the first lithium-containing metal body 1 covered by the two side membranes is a slow-release lithium supplementing region H, and the upper part of the first lithium-containing metal body 1 not covered by the two side membranes is a first-effect lithium supplementing region S. The area ratio of the first-effect lithium supplement area S to the slow-release lithium supplement area H is 1/5.
Fig. 2(a) and 2(b) are an exploded view and an assembled view of a composite lithium supplement sheet according to a second embodiment of the present invention. In the embodiment shown in fig. 2(a) and 2(b), the composite lithium supplement sheet includes a first lithium-containing metal body 1, a first membrane sheet 2, and a second membrane sheet 3. The first lithium-containing metal body 1 is a monolithic structure. The first membrane 2 and the second membrane 3 are made of a mixture of polyvinylidene fluoride and graphene, and micropores are formed in the first membrane 2 and the second membrane 3, wherein the pore diameter of each micropore is 100 mu m, and the porosity of each through hole is 80%. The first membrane 2 and the second membrane 3 are respectively positioned at two sides of the first lithium-containing metal body 1, and when the first membrane 2 and the second membrane 3 are fixedly connected to the first lithium-containing metal body 1, the peripheral edge of the first lithium-containing metal body 1 is not covered. The middle part of the first lithium-containing metal body 1 covered by the two side membranes is a slow-release lithium supplementing area H, and the peripheral edge part of the first lithium-containing metal body 1 not covered by the two side membranes is a first-effect lithium supplementing area S. The area ratio of the first-effect lithium supplement area S to the slow-release lithium supplement area H is 1/2.
Fig. 3(a) and 3(b) are an exploded view and an assembled view of a composite lithium supplement sheet according to a third embodiment of the present invention. In the embodiment shown in fig. 3(a) and 3(b), the composite lithium supplement sheet includes a first lithium containing metal body 1, a first substrate 4, a first membrane sheet 2, and a second membrane sheet 3. The first lithium-containing metal body 1 is a separator structure, a plurality of strip-shaped separators are fixedly connected to the first substrate 4 from both sides of the first substrate 4 in a symmetrical manner, and the material of the first substrate 4 is a composite of polypropylene and carbon black. The first diaphragm 2 and the second diaphragm 3 are made of a mixture of polypropylene and aluminum powder, and the first diaphragm 2 and the second diaphragm 3 are provided with micropores, the pore diameter of each micropore is 1000 microns, and the porosity of each through hole is 50%. The first membrane 2 and the second membrane 3 are respectively positioned at two sides of a first substrate 4 provided with a first lithium-containing metal body 1, and when the first membrane 2 and the second membrane 3 are fixedly connected to the first lithium-containing metal body 1 and the first substrate 4, the upper edge and the lower edge of the first lithium-containing metal body 1 are not covered. The middle part of the first lithium-containing metal body 1 covered by the two side membranes is a slow-release lithium supplementing area H, and the upper edge part and the lower edge part of the first lithium-containing metal body 1 not covered by the two side membranes are first-effect lithium supplementing areas S. The area ratio of the first-effect lithium supplement area S to the slow-release lithium supplement area H is 1/4.
Fig. 4(a) and 4(b) are an exploded view and a combined view of a composite lithium supplement sheet according to a fourth embodiment of the present invention. In the embodiment shown in fig. 4(a) and 4(b), the composite lithium supplement sheet includes a first lithium containing metal body 1, a first membrane sheet 2, and a second membrane sheet 3. The first lithium-containing metal body 1 is a monolithic structure, and the conductive part 5 is fixedly connected to the first lithium-containing metal body 1 in a conductive connection manner. The first membrane 2 and the second membrane 3 are made of polymethyl methacrylate, micropores are formed in the first membrane 2 and the second membrane 3, the pore diameter of each micropore is 1500 mu m, and the porosity of each through hole is 10%. The first diaphragm 2 and the second diaphragm 3 are respectively positioned at two sides of the first lithium-containing metal body 1, a plurality of round openings 6 are respectively arranged on the first diaphragm 2 and the second diaphragm 3, the shape and the position of the opening of the first diaphragm 2 correspond to the shape and the position of the opening of the second diaphragm 3, and the plurality of openings 6 are uniformly distributed on the diaphragms. When the first membrane 2 and the second membrane 3 are fixedly connected to the first lithium-containing metal body 1, the portion of the first lithium-containing metal body 1 corresponding to the opening 6 is not covered. The part of the first lithium-containing metal body 1 covered by the membranes on the two sides is a slow-release lithium supplementing area H, and the part of the first lithium-containing metal body 1 not covered by the membranes on the two sides is a first-effect lithium supplementing area S. The area ratio of the first-effect lithium supplement area S to the slow-release lithium supplement area H is 1/5. The lithium supplementing quantity during the first-effect lithium supplementing can be controlled through the number and the size of the openings 6 in the membrane, and the uniform degree of the first-effect lithium supplementing and the lithium supplementing of the whole life cycle of the battery can be controlled through the arrangement positions of the openings 6.
Fig. 5(a) and 5(b) are an exploded view and an assembled view of a composite lithium supplement sheet according to a fifth embodiment of the present invention. In the embodiment shown in fig. 5(a) and 5(b), the composite lithium supplement sheet includes a first lithium containing metal body 1, a first substrate 4, a first membrane sheet 2, and a second membrane sheet 3. The first lithium-containing metal body 1 is a separation sheet structure, a plurality of strip-shaped separation sheets are fixedly connected to the first substrate 4 from two sides of the first substrate 4, and the first substrate 4 is made of polypropylene. The first membrane 2 and the second membrane 3 are made of a composite of polytetrafluoroethylene and carbon nanotubes, and the first membrane 2 and the second membrane 3 are provided with micropores, the pore diameter of each micropore is 20 micrometers, and the porosity of each through hole is 90%. The first membrane 2 and the second membrane 3 are respectively positioned at two sides of the first lithium-containing metal body 1, a plurality of strip-shaped openings 6 are respectively arranged on the first membrane 2 and the second membrane 3, the shapes and the positions of the openings of the first membrane 2 correspond to those of the openings of the second membrane 3, the positions of the openings 6 are positioned on the strip-shaped first lithium-containing metal body 1, and the openings 6 are uniformly distributed on the membranes. When the first membrane 2 and the second membrane 3 are fixedly connected to the first lithium-containing metal body 1, a portion of the upper side of the first lithium-containing metal body 1 and a portion corresponding to the opening 6 are not covered. The part of the first lithium-containing metal body 1 covered by the membranes on the two sides is a slow-release lithium supplementing area H, and the part of the first lithium-containing metal body 1 not covered by the membranes on the two sides is a first-effect lithium supplementing area S. The area ratio of the first-effect lithium supplement area S to the slow-release lithium supplement area H is 1/3.
Fig. 6(a) and 6(b) are an exploded view and an assembled view of a composite lithium supplement sheet according to a sixth embodiment of the present invention. In the embodiment shown in fig. 6(a) and 6(b), the composite lithium supplement sheet includes a first lithium-containing metal body 1, a second lithium-containing metal body 7, a first membrane 2, and a second membrane 3. The first lithium-containing metal body 1 is a monolithic structure. The first membrane 2 and the second membrane 3 are made of a mixture of polyethylene oxide and conductive carbon black, and the first membrane 2 and the second membrane 3 are provided with micropores, the pore diameter of each micropore is 400 mu m, and the porosity of each through hole is 65%. The first membrane 2 and the second membrane 3 are respectively positioned at two sides of the first lithium-containing metal body 1, and the first membrane 2 and the second membrane 3 completely cover the first lithium-containing metal body 1, namely the whole first lithium-containing metal body 1 is a slow-release lithium supplementing area H. Two second lithium-containing metal bodies 7 are located outside the first membrane 2 and the second membrane 3, respectively. A plurality of circular through holes 8 are provided on the second lithium-containing metal body 7, and the positions of the plurality of through holes 8 are uniformly distributed on the second lithium-containing metal body 7. The whole first lithium-containing metal body 1 covered by the diaphragms on the two sides is a slow-release lithium supplement area H, and the second lithium-containing metal body 7 not covered by the diaphragms is a first-effect lithium supplement area S. In the first lithium supplement process, the second lithium-containing metal body 7 is almost completely exhausted, and in the subsequent lithium supplement process, the first lithium-containing metal body 1 is slowly released through the micropores of the membrane. The area ratio of the first-effect lithium supplement area S to the slow-release lithium supplement area H is 1/2. The lithium supplementing quantity during the first effective lithium supplementing can be controlled through the number and the size of the through holes 8 in the second lithium-containing metal body 7, and the uniformity during the first effective lithium supplementing can be controlled through the arrangement positions of the through holes 8.
Fig. 7(a) and 7(b) are an exploded view and a combined view of a composite lithium supplement sheet according to a seventh embodiment of the present invention. In the embodiment shown in fig. 7(a) and 7(b), the composite lithium supplement sheet includes a first lithium-containing metal body 1, a second lithium-containing metal body 7, a second substrate 9, a first membrane 2, and a second membrane 3. The first lithium-containing metal body 1 is a monolithic structure. The first membrane 2 and the second membrane 3 are made of a mixture of polyethylene terephthalate and graphene, and the first membrane 2 and the second membrane 3 are provided with micropores, the pore diameter of each micropore is 800 micrometers, and the porosity of each through hole is 45%. The first membrane 2 and the second membrane 3 are respectively positioned at two sides of the first lithium-containing metal body 1, and the first membrane 2 and the second membrane 3 completely cover the first lithium-containing metal body 1, namely the whole first lithium-containing metal body 1 is a slow-release lithium supplementing area H. The second lithium-containing metal bodies 7 with a plurality of separation sheet structures are fixedly connected to the second substrate 9, a plurality of separation sheets are uniformly distributed on the second substrate 9, and the two second substrates 9 provided with the second lithium-containing metal bodies 7 are respectively positioned at the outer sides of the first membrane 2 and the second membrane 3. The second substrate 9 is a porous structure. The integral first lithium-containing metal body 1 covered by the two side diaphragms and the second substrate is a slow-release lithium supplementing area H, and the second lithium-containing metal body 7 not covered by the diaphragms is a first-effect lithium supplementing area S. In the first lithium replenishing process, the second lithium-containing metal body 7 is almost completely consumed, and in the subsequent lithium replenishing process, the first lithium-containing metal body 1 is slowly released through the micropores of the membrane and the holes of the second substrate 9. The area ratio of the first-effect lithium supplement area S to the slow-release lithium supplement area H is 1/4. The lithium supplementing amount during the first-effect lithium supplementing can be controlled through the number and the size of the separating sheets of the second lithium-containing metal body 7, and the uniformity during the first-effect lithium supplementing can be controlled through the arrangement positions of the separating sheets.
Fig. 8(a) and 8(b) are an exploded view and a combined view of a composite lithium supplement sheet according to an eighth embodiment of the present invention. In the embodiment shown in fig. 8(a) and 8(b), the composite lithium supplement sheet includes a first lithium-containing metal body 1, a second lithium-containing metal body 7, a first membrane 2, and a second membrane 3. The first lithium-containing metal body 1 is a monolithic structure. The first membrane 2 and the second membrane 3 are made of a mixture of polysiloxane and carbon nano tubes, and the first membrane 2 and the second membrane 3 are provided with micropores, the pore diameter of each micropore is 2000 mu m, and the porosity of each through hole is 15%. The first membrane 2 and the second membrane 3 are respectively positioned at two sides of the first lithium-containing metal body 1, and the first membrane 2 and the second membrane 3 completely cover the first lithium-containing metal body 1, namely the whole first lithium-containing metal body 1 is a slow-release lithium supplementing area H. The second lithium-containing metal bodies 7 with two curve-shaped strip structures are respectively positioned at the outer sides of the first diaphragm 2 and the second diaphragm 3, and curves are uniformly distributed in the whole area of the electrode plate. The whole first lithium-containing metal body 1 covered by the diaphragms on the two sides is a slow-release lithium supplement area H, and the second lithium-containing metal body 7 not covered by the diaphragms is a first-effect lithium supplement area S. In the first lithium supplement process, the second lithium-containing metal body 7 is almost completely exhausted, and in the subsequent lithium supplement process, the first lithium-containing metal body 1 is slowly released through the micropores of the membrane. The area ratio of the first-effect lithium supplement area S to the slow-release lithium supplement area H is 1/3. The uniformity in the first lithium supplement can be controlled by the curve shape of the uniform arrangement of the second lithium-containing metal body 7.
Fig. 9 is a partially exploded view of a battery cell according to a first embodiment of the present invention. The battery core comprises a positive plate 10, a negative plate 11, an isolation layer 12 and composite lithium supplement plates 13a and 13 b. The positive electrode sheet 10 and the negative electrode sheet 11 are alternately laminated, and the separator 12 is provided between the positive electrode sheet 10 and the negative electrode sheet 11. The positive active material layer and the positive current collector of the positive plate 10 adopt a porous structure, and the negative active material layer and the negative current collector of the negative plate 11 adopt a porous structure. In this embodiment, a composite lithium supplement sheet is provided in each positive electrode sheet 10. In two adjacent positive electrode plates 10, a first composite lithium supplement plate 13a and a second composite lithium supplement plate 13b can be respectively arranged. The first composite lithium supplement sheet 13a and the second composite lithium supplement sheet 13b each include a first lithium-containing metal body, a first membrane, and a second membrane. The first membrane and the second membrane are located on both sides of the first lithium-containing metal body. In the first composite lithium supplement sheet 13a, the first lithium-containing metal body 1a is of a whole-piece structure, a plurality of strip-shaped openings are arranged on the first membrane 2a and the second membrane 3a, a slow-release lithium supplement area H1 of the first composite lithium supplement sheet 13a is formed by the part covered by the first membrane 2a and the second membrane 3a, and a first-effect lithium supplement area S1 of the first composite lithium supplement sheet 13a is formed by the part not covered by the first membrane 2a and the second membrane 3 a. In the second composite lithium supplement sheet 13b, the first lithium-containing metal body 1b is of a whole sheet structure, a plurality of strip-shaped openings are arranged on the first membrane 2b and the second membrane 3b, a slow-release lithium supplement area H2 of the second composite lithium supplement sheet 13b is formed by the part covered by the first membrane 2b and the second membrane 3b, and a first-effect lithium supplement area S2 of the second composite lithium supplement sheet 13b is formed by the part not covered by the first membrane 2b and the second membrane 3 b. The strip-shaped slow-release lithium supplementing region H1 of the first composite lithium supplementing sheet 13a and the strip-shaped slow-release lithium supplementing region H2 of the second composite lithium supplementing sheet 13b are staggered with each other, and the strip-shaped first-effect lithium supplementing region S1 of the first composite lithium supplementing sheet 13a and the strip-shaped first-effect lithium supplementing region S2 of the second composite lithium supplementing sheet 13b are staggered with each other. For each positive plate, in the process of first-effect lithium supplement or long-term lithium supplement, the lithium can be supplemented uniformly on the whole surface of the positive plate through direct lithium supplement of the adjacent composite lithium supplement plate and remote lithium supplement of the farther composite lithium supplement plate penetrating through the porous structure.
Fig. 10 is a partially exploded view of a battery cell according to a second embodiment of the present invention. The battery core comprises a positive plate 10, a negative plate 11, an isolation layer 12 and composite lithium supplement plates 13a and 13 b. The positive electrode sheet 10 and the negative electrode sheet 11 are alternately laminated, and the separator 12 is provided between the positive electrode sheet 10 and the negative electrode sheet 11. The positive active material layer and the positive current collector of the positive plate 10 adopt a porous structure, and the negative active material layer and the negative current collector of the negative plate 11 adopt a porous structure. In the embodiment, one or more positive electrode plates without the composite lithium supplement plate are arranged between the two positive electrode plates with the composite lithium supplement plate. In two adjacent positive electrode plates 10 provided with the composite lithium supplement plates, a first composite lithium supplement plate 13a and a second composite lithium supplement plate 13b can be respectively provided. The first composite lithium supplement sheet 13a and the second composite lithium supplement sheet 13b each include a first lithium-containing metal body, a first substrate, a first membrane, and a second membrane. The first lithium-containing metal body is fixedly connected to the first substrate, and the first membrane and the second membrane are positioned on two sides of the first substrate. In the first composite lithium supplementing sheet 13a, the first lithium-containing metal body 1a is a plurality of strip-shaped separating sheets, the separating sheets are uniformly distributed on the first substrate 4a, the first membrane 2a and the second membrane 3a cover the middle lower part of the first lithium-containing metal body 1a, the part covered by the first membrane 2a and the second membrane 3a forms a slow-release lithium supplementing area H1 of the first composite lithium supplementing sheet 13a, and the part not covered by the first membrane 2a and the second membrane 3a forms a first-effect lithium supplementing area S1 of the first composite lithium supplementing sheet 13 a. In the second composite lithium supplementing sheet 13b, the first lithium-containing metal body 1b is a plurality of strip-shaped separating sheets, the separating sheets are uniformly distributed on the first substrate 4b, the first membrane 2b and the second membrane 3b cover the middle upper part of the first lithium-containing metal body 1b, the part covered by the first membrane 2b and the second membrane 3b forms a slow-release lithium supplementing area H2 of the second composite lithium supplementing sheet 13b, and the part not covered by the first membrane 2b and the second membrane 3b forms a first-effect lithium supplementing area S2 of the second composite lithium supplementing sheet 13 b. The first-effect lithium supplement region S1 of the first composite lithium supplement sheet 13a and the first-effect lithium supplement region S2 of the second composite lithium supplement sheet 13b are staggered with each other in the transverse position and the uncovered part of the separation sheet. For each positive plate, lithium can be directly supplemented by the adjacent composite lithium supplementing plate and lithium can be remotely supplemented by the farther composite lithium supplementing plate penetrating through the porous structure, so that more uniform lithium supplementation on the whole surface of the positive plate can be realized.
The specific embodiments of the present invention are not intended to be limiting of the invention. Those skilled in the art can make numerous possible variations and modifications to the present invention, or modify equivalent embodiments, using the methods and techniques disclosed above, without departing from the scope of the present invention. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (14)
1. A composite lithium supplementing sheet is characterized by comprising a first membrane, a second membrane and a first lithium-containing metal body, the first membrane and the second membrane are symmetrical in structure, the first membrane and the second membrane are arranged on two sides of the first lithium-containing metal body, the first membrane and the second membrane cover the area of the first lithium-containing metal body from two sides to form a slow-release lithium supplementing area of the composite lithium supplementing sheet, the first membrane and the second membrane do not cover the area of the first lithium-containing metal body from two sides to form a first-effect lithium supplementing area of the composite lithium supplementing sheet, the first membrane and the second membrane are provided with micropores, the pore diameter of the micropores is 0.01-2000 mu m, the porosity of the through holes of the micropores is 10% -90%, and the area ratio of the first-effect lithium supplement area to the slow-release lithium supplement area is 1/2-1/5; or, the composite lithium supplementing sheet comprises a first membrane, a second membrane, a first lithium-containing metal body and a second lithium-containing metal body, the first membrane and the second membrane are symmetrical in structure, the first membrane and the second membrane are arranged on two sides of the first lithium-containing metal body, the second lithium-containing metal body is arranged on the outer sides of the first membrane and the second membrane, the first membrane and the second membrane cover the first lithium-containing metal body from two sides to form a slow-release lithium supplementing area of the composite lithium supplementing sheet, the second lithium-containing metal body area and the first membrane and the second membrane do not cover the first lithium-containing metal body from two sides to form a first-effect lithium supplementing area of the composite lithium supplementing sheet, the first membrane and the second membrane are provided with micropores, the pore diameter of the micropores is 0.01 μm-2000 μm, and the porosity of through holes of the micropores is 10% -90%, the area ratio of the first-effect lithium supplementing area to the slow-release lithium supplementing area is 1/2-1/5.
2. The composite lithium patch of claim 1, wherein the first lithium-containing metal body is a monolithic structure; alternatively, the first lithium-containing metal body is in a structure of a plurality of separation sheets, and the plurality of separation sheets are partially connected or spaced apart from each other.
3. The composite lithium supplement sheet according to claim 1 or 2, wherein an opening is formed in the first membrane and the second membrane, the opening is curved, and the opening is uniformly distributed on the first membrane and the second membrane; or a plurality of openings are arranged on the first membrane and the second membrane, the openings are circular, oval, curved or polygonal, and the plurality of openings are uniformly distributed on the first membrane and the second membrane.
4. The composite lithium patch of claim 1 or 2, wherein the composite lithium patch further comprises a first substrate to which the first lithium-containing metal body is fixedly attached.
5. The composite lithium supplement sheet according to claim 1 or 2, wherein the second lithium-containing metal body is a monolithic structure, a through hole is formed in the second lithium-containing metal body, the through hole is in a curved shape, and the through holes are uniformly distributed on the second lithium-containing metal body; or, a plurality of through holes are arranged on the second lithium-containing metal body, the through holes are circular, elliptical, curved or polygonal, and the through holes are uniformly distributed on the second lithium-containing metal body.
6. The composite lithium supplement sheet according to claim 1 or 2, wherein the second lithium-containing metal body is a structure of a plurality of separation sheets, and the separation sheets are partially connected or spaced apart from each other.
7. The composite lithium patch of claim 1 or 2, wherein the second lithium-containing metal body is a strip structure having a uniformly distributed curve.
8. The composite lithium patch of claim 1 or 2, wherein the composite lithium patch further comprises a second substrate to which the second lithium-containing metal body is fixedly attached, the second substrate being a porous structure.
9. The composite lithium supplement sheet according to claim 1 or 2, wherein the first membrane sheet and the second membrane sheet are polymer conductive layers made of a composite or a mixture of a polymer and a conductive material, the polymer is polyethylene, polypropylene, a polyethylene-propylene copolymer, polytetrafluoroethylene, polyethylene terephthalate, polypyrrole, polyvinylidene fluoride, a polyvinylidene fluoride-hexafluoropropylene copolymer, polymethyl methacrylate, polyethylene oxide, aliphatic polycarbonate or polysiloxane, and the conductive material is a conductive carbon material or a conductive metal material.
10. The composite lithium supplement sheet according to claim 1 or 2, wherein the first membrane and the second membrane are insulating layers, the insulating layers are made of polymers or composites of polymers and inorganic non-metallic materials, the polymers are polyethylene, polypropylene, polyethylene-propylene copolymers or polytetrafluoroethylene, the inorganic non-metallic materials are aluminum oxide or silicon dioxide, and the composite lithium supplement sheet further comprises a conductive part, and the conductive part is used for electrically connecting the slow-release lithium supplement region of the composite lithium supplement sheet with a positive tab of a battery or with a negative tab of the battery.
11. A battery cell, wherein the battery cell comprises a positive plate, a negative plate, an isolation layer and the composite lithium supplement plate according to any one of claims 1 to 10, the positive plate and the negative plate are stacked in a crossed manner, the isolation layer is arranged between the positive plate and the negative plate, and the composite lithium supplement plate is arranged inside the positive plate or between the positive plate and the isolation layer; or the composite lithium supplement sheet is arranged inside the negative electrode sheet or between the negative electrode sheet and the isolation layer.
12. The battery cell of claim 11, wherein the positions of the slow-release lithium supplement regions of two adjacent composite lithium supplement sheets are staggered with each other.
13. The cell of claim 11 or 12, wherein the locations of the first-effect lithium supplement regions of two adjacent composite lithium supplement sheets are staggered with respect to each other.
14. A battery comprising a housing and the cell of any of claims 11 to 13.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN116053708A (en) * | 2023-03-29 | 2023-05-02 | 安迈特科技(北京)有限公司 | Lithium supplementing composite diaphragm for lithium battery, lithium battery and preparation method of lithium battery |
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