CN114284463B - Composite lithium supplementing sheet and battery cell and battery provided with same - Google Patents
Composite lithium supplementing sheet and battery cell and battery provided with same Download PDFInfo
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- CN114284463B CN114284463B CN202011030722.3A CN202011030722A CN114284463B CN 114284463 B CN114284463 B CN 114284463B CN 202011030722 A CN202011030722 A CN 202011030722A CN 114284463 B CN114284463 B CN 114284463B
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- lithium
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- containing metal
- metal body
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 443
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 443
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 182
- 239000002131 composite material Substances 0.000 title claims abstract description 141
- 239000012528 membrane Substances 0.000 claims abstract description 233
- 229910052751 metal Inorganic materials 0.000 claims abstract description 189
- 239000002184 metal Substances 0.000 claims abstract description 189
- 238000013268 sustained release Methods 0.000 claims abstract description 11
- 239000012730 sustained-release form Substances 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims description 52
- -1 polyethylene Polymers 0.000 claims description 47
- 229920000642 polymer Polymers 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 239000004743 Polypropylene Substances 0.000 claims description 11
- 239000004020 conductor Substances 0.000 claims description 11
- 229920001155 polypropylene Polymers 0.000 claims description 11
- 239000004698 Polyethylene Substances 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
- 238000002955 isolation Methods 0.000 claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 7
- 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
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 3
- 239000007769 metal material Substances 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
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 238000010276 construction Methods 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
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 25
- 230000007774 longterm Effects 0.000 abstract description 9
- 238000003487 electrochemical reaction Methods 0.000 abstract description 3
- 239000013589 supplement Substances 0.000 description 28
- 210000004027 cell Anatomy 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 238000000926 separation method Methods 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 7
- 230000009469 supplementation Effects 0.000 description 7
- 239000002041 carbon nanotube Substances 0.000 description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 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
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 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
- 239000000843 powder Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 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
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000002788 crimping Methods 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation 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
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 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
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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 diaphragm, a second diaphragm 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 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 effective lithium supplementing area for quickly supplementing active lithium consumed by forming an SEI film in the first charge and discharge process of the battery; the portion of the lithium-containing metal body covered by the first and second membranes forms a sustained release lithium replenishment zone for permanently replenishing active lithium lost by the battery during the long-term electrochemical reaction. The composite lithium supplementing sheet can simultaneously realize first-effect lithium supplementing and long-term lithium supplementing of the battery, can control the lithium supplementing amount in the first-effect lithium supplementing process and the lithium supplementing amount of the battery in the long-term use process, ensures sufficient active lithium supplementing of the battery, and avoids potential safety hazards caused by excessive lithium supplementing.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to a composite lithium supplementing sheet, and an electric core and a battery provided with the composite lithium supplementing 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 generation of 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 cathode Solid Electrolyte Interface (SEI) film, and in the first charging process of lithium ion battery formation, the SEI film formed on the surface of the cathode consumes part of active lithium to cause lithium loss of a cathode material, the first charging of a common graphite cathode consumes about 10% of a lithium source, and the more the cathode material with higher specific capacity, such as silicon, amorphous carbon and the like, consumes more cathode lithium source; in addition, active lithium is continuously consumed in the continuous operation process of the battery except for the first charge and discharge process, so that capacity attenuation after circulation is caused.
The lithium supplementing of the positive electrode or the negative electrode is an effective method for improving the energy density and the cycle performance of the lithium ion battery, and is an important point of the lithium supplementing technology research of the lithium ion battery, so that the first effect is improved, and meanwhile, the consumption of active lithium can be continuously supplemented in the battery cycle process. There have been studies to compensate capacity loss of lithium ion batteries in the first charge and discharge by introducing metal lithium (powder) or metal lithium salt having higher activity, but this method can only supplement loss of the battery in the first charge process, and has limited effect of improving cycle life after multiple cycles. In addition, the first effect lithium supplementation of the battery and the continuous lithium supplementation in the operation process are realized by introducing the third electrode, but the cell structure and the shell cover structure are required to be redesigned by introducing the third electrode, so that a series of process variations and the like are caused.
Disclosure of Invention
In view of the above problems, the present invention provides a composite lithium-supplementing 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 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 effective lithium supplementing area for quickly supplementing active lithium consumed by forming an SEI film in the first charge and discharge process of the battery; the portion of the lithium-containing metal body covered by the first and second membranes forms a sustained release lithium replenishment zone for permanently replenishing active lithium lost by the battery during the long-term electrochemical reaction. The composite lithium supplementing sheet can simultaneously realize first-effect lithium supplementing and long-term lithium supplementing of the battery, can control the lithium supplementing amount in the first-effect lithium supplementing process and the lithium supplementing amount of the battery in the long-term use process, ensures sufficient active lithium supplementing of the battery, and avoids potential safety hazards caused by excessive lithium supplementing.
The technical scheme provided by the invention is as follows:
the invention provides a composite lithium supplementing 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 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 effective 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 through hole porosity of the micropores is 10-90%, and the area ratio of the first effective lithium supplementing area to the slow-release lithium supplementing 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, 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 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 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 0.01-2000 mu m, the through hole porosity of the micropores is 10-90%, and the area ratio of the first-effect lithium supplementing area to the slow-release lithium supplementing 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 membrane and the second membrane sandwich the first lithium-containing metal body, and a part of the first lithium-containing metal body is covered by the first membrane and the second membrane from both sides, while the remaining part of the first lithium-containing metal body is not covered by the first membrane and the second membrane from both sides. 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 diaphragm and the second diaphragm sandwich the first lithium-containing metal body, and the first diaphragm and the second diaphragm may entirely or partially cover the first lithium-containing metal body, and the other sides of the first diaphragm and the second diaphragm opposite to the immediately adjacent first lithium-containing metal body are provided with the second lithium-containing metal body, respectively, which is not covered by the first diaphragm and the second diaphragm. The lithium-containing metal body not covered by the membrane can be rapidly intercalated or deposited on the electrode active material, thereby playing a role in first-effect lithium supplementation of the battery in the battery formation and the previous lithium supplementation charge-discharge processes. After the lithium-containing metal body which is not covered by the membrane is completely reacted, lithium ions are slowly released through micropores of the membrane after the lithium-containing metal body which is covered by the membrane loses electrons, and are continuously inserted into or deposited on the electrode active material in the whole life cycle of the battery, so that the effect of long-acting lithium supplementation in the whole life cycle of the battery is achieved. The area and ratio of the first-effect lithium-supplementing region not covered by the membrane to the slow-release lithium-supplementing region covered by the membrane can be determined according to the first-effect lithium-supplementing and the lithium-supplementing amount of the whole life cycle lithium-supplementing.
The first lithium-containing metal body may be of unitary construction, i.e., the first lithium-containing metal body may be a unitary sheet. The first lithium-containing metal body may also be in a plurality of separator structures, with portions of the separator structures being connected or spaced apart from each other, when the first lithium-containing metal body in the whole sheet would cause the amount of lithium to be replenished in excess of the desired amount. The plurality of separator structures disposed in the middle of the composite lithium supplementing sheet are collectively referred to as a first lithium-containing metal body. When the plurality of separator sheets are spaced apart from each other, it is preferable that each separator sheet is connected by a connection portion or connected by a base sheet to form an integral structure, so that the process of preparing the composite lithium-supplementing sheet using the first lithium-containing metal is easier to operate.
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 in the first and second diaphragms, which may be curved, such as S-shaped, zig-zag shaped, or spiral. Preferably, the openings are uniformly distributed 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 in the first and second diaphragms, and the openings may be circular, elliptical, curved, polygonal, or the like. Preferably, the plurality of openings are uniformly distributed over the first and second membranes, that is, the plurality of openings are substantially uniformly distributed at the corners and central regions of the membranes, with substantially the same spacing between the openings. Through evenly laying the opening on the diaphragm, can make the deposition or the interior active lithium of embedding pole piece appear evenly distributed to ensure the even lithium filling of whole pole piece, avoid the potential safety hazard such as lithium dendrite puncture diaphragm that the excessive lithium filling of part caused.
The composite lithium supplementing sheet may further include a first substrate, and the first lithium-containing metal body may be fixedly connected to the first substrate. In the case where the first lithium-containing metal body is a thin foil or a structure of a plurality of separate pieces, the first lithium-containing metal body is preferably fixedly connected to the first substrate by, for example, press-fitting or bonding, whereby problems such as difficult processing and assembly due to curling of the foil or dispersion of the separate pieces can be avoided. The first substrate can be provided with a through hole, or the two sides of the first substrate are respectively provided with a first lithium-containing metal body, so that the electrode active materials positioned at the two sides of the composite lithium supplementing sheet can be simultaneously supplemented 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 a polymer such as polyethylene, polypropylene, polyethylene-propylene copolymer, polytetrafluoroethylene, polyethylene terephthalate, or the like. Alternatively, the first substrate may be electrically conductive, for example, the material of the first substrate may be a composite or mixture of a polymer and an electrically conductive material, wherein the polymer may be a polymer electrochemically stable in an electrolyte such as polyethylene, polypropylene, polyethylene-propylene copolymer, polytetrafluoroethylene, polyethylene terephthalate, polypyrrole, etc., and the electrically conductive material may be carbon black, carbon nanotubes, graphene, electrically conductive metal powder, etc.; alternatively, the first substrate may be a conductive material such as copper, aluminum, etc., and the substrate may serve to both collect 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 on the outer side of the diaphragm. 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 by the membrane, with the portion of the first lithium-containing metal body not covered by the membrane and the second lithium-containing metal body acting together as the first-effect lithium-replenishment region. The second lithium-containing metal body may have a monolithic structure, and a through hole may be formed in the second lithium-containing metal body, and the through hole may have a curved shape such as an S-shape, a zigzag shape, or a spiral shape, and the through hole is uniformly formed in the second lithium-containing metal body; alternatively, the second lithium-containing metal body may be provided with a plurality of through holes, and the through holes may be circular, elliptical, curved, polygonal, or the like, and the plurality of through holes may be uniformly disposed on the second lithium-containing metal body. The lithium supplementing amount can be controlled by setting the size of the through hole, so that the situation of excessive lithium supplementing is avoided; the through holes are uniformly arranged, so that uniform lithium supplement of the whole pole piece can be ensured, and the situation of local excessive lithium supplement is avoided. The second lithium-containing metal body may also be a plurality of separator structures, with portions of the plurality of separators being connected or spaced apart from one another. The lithium supplementing amount can be controlled by setting the size of the separation sheet, and the purpose of uniformly supplementing lithium can be achieved by uniformly arranging the separation sheet. The second lithium-containing metal body may have a uniformly distributed elongated structure such as a curve, and the curve may be, for example, S-shaped, zigzag-shaped, spiral-shaped, or the like.
The composite lithium supplementing sheet can further comprise a second substrate, and the second lithium-containing metal body is fixedly connected to the second substrate. In the case where the second lithium-containing metal body is a thin foil, a plurality of separate pieces, or a long strip, it is preferable that the second lithium-containing metal body is fixedly connected to the second substrate by, for example, press-fitting or bonding, so that the problem of difficult processing and assembly due to curling of the foil, the long strip, or dispersion of the separate pieces can be avoided. The second substrate is porous so that active lithium of the first lithium-containing metal body can diffuse smoothly out through the membrane and the second substrate. The material of the second substrate may be a material stable in structure in the electrolyte, may be conductive or nonconductive, for example, may be a polymer such as polyethylene, polypropylene, polyethylene-propylene copolymer, polytetrafluoroethylene, polyethylene terephthalate, or the like, or may be a composite or mixture of a polymer and a conductive material, wherein the polymer may be a polymer which is electrochemically stable in the electrolyte, such as polyethylene, polypropylene, polyethylene-propylene copolymer, polytetrafluoroethylene, polyethylene terephthalate, polypyrrole, or the like, and the conductive material may be carbon black, carbon nanotubes, graphene, conductive metal powder, or the like. When the second substrate is a conductive material such as copper, aluminum, etc., the substrate may serve to both collect and conduct current. When the second lithium-containing metal body is in a foil, strip structure or separation sheet structure, the second lithium-containing metal body can also be directly and fixedly connected with 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, and the material of the polymer conductive layers may be a composite or mixture of a polymer and a conductive material, wherein the polymer may be a polymer which is electrochemically stable in an electrolyte, such as polyethylene, polypropylene, polyethylene-propylene copolymer, polytetrafluoroethylene, polyethylene terephthalate, polypyrrole, and the like, preferably a gel polymer material, such as polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene copolymer, polymethyl methacrylate, polyethylene oxide, aliphatic polycarbonate, polysiloxane, and the like, and the conductive material may be a conductive carbon material or a conductive metal material, such as conductive carbon black, graphene, carbon nanotubes, aluminum powder, copper powder, and the like, and the conductivity of the first and second membranes may be controlled to be 0 to 5000S/cm by the doping ratio of the conductive filler. Because metallic lithium conductivity is very good, after the area not covered by the membrane is directly connected with the electrode, the reaction can be quickly carried out when the battery is charged and discharged, lithium loss caused by SEI film generation or side reaction is supplemented, after the reaction of the uncovered area is finished, the area covered by the first membrane and the second membrane is electrically connected with the electrode through the first membrane and the second membrane, the electric conductivity of the first membrane and the second membrane can be controlled, and the speed of the electron on the surface of the metallic lithium can be controlled, so that the reaction of the metallic lithium is controlled, and the active lithium lost by the battery reaction is slowly supplemented. The first and second membranes may also be insulating layers, the material of which may be a polymer material that is non-conductive and electrochemically stable in the electrolyte or may be a composite of a polymer, such as polyethylene, polypropylene, polyethylene-propylene copolymer or polytetrafluoroethylene, and an inorganic non-metallic material, such as alumina or silica. The composite lithium supplementing sheet can further comprise a conductive part, wherein the conductive part can be a conductive wire, a conductive sheet and the like, and the conductive part can be electrically connected with the slow release lithium supplementing region 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 conducting connection between a slow-release lithium supplementing area of the composite lithium supplementing sheet and a positive electrode lug of a battery or a negative electrode lug of the battery, and after the reaction of the area, which is not covered by the diaphragm, of metal lithium is completed, lithium ions can be slowly released by the area covered by the diaphragm through micropores of the diaphragm, so that the metal lithium is controlled to play a role in continuously supplementing lithium; if the first membrane, the second membrane or the first substrate in contact with the first lithium-containing metal body is a conductive material, the conductive portion may be electrically connected to the positive electrode tab or the negative electrode tab, or the conductive portion may be electrically connected to 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 then 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 isolating layer and the composite lithium supplementing plate. The positive plate and the negative plate are alternately laminated, the isolation layer is arranged between the positive plate and the negative plate, and the composite lithium supplementing 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 electrode sheet or between the negative electrode sheet and the isolation layer. The composite lithium supplementing sheet can be arranged in each positive electrode sheet or each negative electrode sheet. In the case where the positive electrode sheet and the negative electrode sheet are porous electrode sheets, the composite lithium supplementing sheet may be disposed in two positive electrode sheets with other positive electrode sheets interposed therebetween or in two negative electrode sheets with other negative electrode sheets interposed therebetween. And the lithium supplementing of all the electrode plates is realized by the diffusion of active lithium in the porous electrode battery.
Preferably, the positions of the slow release lithium supplementing areas of two adjacent composite lithium supplementing tablets are staggered. Thus, more uniform lithium supplement of the whole electrode plate area in the long-term lithium supplement process can be ensured. More preferably, the positions of the sustained-release lithium-supplementing regions of two adjacent composite lithium-supplementing tablets are complementary. Specifically, in the case that the sustained-release lithium-supplementing region does not cover the whole electrode sheet, the sustained-release lithium-supplementing regions of two adjacent composite lithium-supplementing sheets may take a complementary form, the sustained-release lithium-supplementing region of one composite lithium-supplementing sheet corresponds to the non-sustained-release lithium-supplementing region of the other composite lithium-supplementing sheet, and the non-sustained-release lithium-supplementing region of one composite lithium-supplementing sheet corresponds to the sustained-release lithium-supplementing region of the other composite lithium-supplementing sheet, so that in the long-term lithium supplementing process, the overall and uniform lithium supplementation of the whole electrode sheet region can be ensured.
Preferably, the first effective lithium supplementing areas of two adjacent composite lithium supplementing sheets are staggered. Thus, more uniform lithium supplement of the whole electrode plate area in the first-effect lithium supplement process can be ensured. More preferably, the locations of the first-effect lithium-replenishing regions of two adjacent composite lithium-replenishing sheets are complementary. 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 plates can adopt a complementary form, the first-effect lithium supplementing area of one composite lithium supplementing plate corresponds to the non-first-effect lithium supplementing area of the other composite lithium supplementing plate, and the non-first-effect lithium supplementing area of one composite lithium supplementing plate corresponds to the first-effect lithium supplementing area of the other composite lithium supplementing plate, 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, a battery is further provided, and comprises a shell and the battery cell, wherein the battery cell is provided with the composite lithium supplementing sheet. In the preparation process of the battery cell, the composite lithium supplementing sheet is placed in the electrode sheet or is closely adjacent to the electrode sheet. And (3) accommodating the prepared battery cell into a shell, and injecting electrolyte to perform a formation reaction. Since side reactions such as SEI film are generated at the negative electrode during the first charge and discharge of the battery, consumption of part of active lithium is caused. Active lithium in a first-effect lithium supplementing region of the composite lithium supplementing sheet can be rapidly deposited on or embedded into an electrode active material of the electrode sheet, so that the lost active lithium 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 electrochemical reaction process of the battery, active lithium in a slow-release lithium supplementing region of the composite lithium supplementing sheet can be slowly released through micropores of the membrane and continuously deposited on or embedded into an electrode active material of the electrode sheet, so that long-time active lithium supplementing can be realized. The battery provided by the invention can realize first-effect lithium supplement and continuous lithium supplement of the whole life cycle.
In the present invention, words of up, down, left, right, and the like, which represent directions are words of description only for clarity, and do not serve as limitations.
The invention has the advantages that:
1) The lithium supplementing sheet structure has a dual-function lithium supplementing area, and the lithium ion slow release is realized by arranging the microporous membrane layer on the surface of the lithium-containing metal body and controlling the conductivity, the microporous parameters and the through hole area of the membrane, so that the active lithium is slowly released in the follow-up operation except the initial effect of the battery, the lithium supplementing of the full life cycle of the battery is realized, and the cycle performance of the battery is effectively improved;
2) Through the design of the positions and the structures of the lithium-containing metal bodies in the single composite lithium supplementing sheet and the adjacent composite lithium supplementing sheets, the uniform intercalation of lithium ions on the porous electrode is realized, and the uniform lithium supplementation of the whole battery is further realized.
Drawings
Fig. 1 (a) and 1 (b) are an exploded view and a combined view of a composite lithium-compensating sheet according to a first embodiment of the present invention;
fig. 2 (a) and 2 (b) are an exploded view and a combined view of a composite lithium-compensating sheet according to a second embodiment of the present invention;
fig. 3 (a) and 3 (b) are an exploded view and a combined view of a composite lithium-compensating sheet according to a third embodiment of the present invention;
fig. 4 (a) and 4 (b) are an exploded view and a combined view of a composite lithium-compensating sheet according to a fourth embodiment of the present invention;
fig. 5 (a) and 5 (b) are an exploded view and a combined view of a composite lithium-compensating sheet according to a fifth embodiment of the present invention;
fig. 6 (a) and 6 (b) are an exploded view and a combined view of a composite lithium-compensating sheet according to a sixth embodiment of the present invention;
fig. 7 (a) and 7 (b) are an exploded view and a combined view of a composite lithium-compensating sheet according to a seventh embodiment of the present invention;
fig. 8 (a) and 8 (b) are an exploded view and a combined view of a composite lithium-compensating 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 and H2-slow-release lithium supplementing area
S, S1, S2-first effect lithium supplementing 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 electrode plate
12-isolation layer
13 a-first composite lithium supplementing sheet
13 b-second composite lithium supplementing tablet
Detailed Description
The invention will be further illustrated by way of example with reference to the accompanying drawings.
Fig. 1 (a) and 1 (b) are an exploded view and a combined view of a composite lithium-compensating sheet according to a first embodiment of the present invention. In the embodiment shown in fig. 1 (a) and 1 (b), the composite lithium supplementing sheet includes a first lithium-containing metal body 1, a first membrane 2, and a second membrane 3. The first lithium-containing metal body 1 is of 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 the micropores is 1 mu m, and the porosity of the through holes is 30%. The first membrane 2 and the second membrane 3 are respectively located at both 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, a portion of the upper side of the first lithium-containing metal body 1 is uncovered. The middle lower part of the first lithium-containing metal body 1 covered by the diaphragms at the two sides is a slow-release lithium supplementing area H, and the upper part of the first lithium-containing metal body 1 not covered by the diaphragms at the two sides is a first effective lithium supplementing area S. The area ratio of the first-effect lithium supplementing region S to the slow-release lithium supplementing region H is 1/5.
Fig. 2 (a) and 2 (b) are an exploded view and a combined view of a composite lithium-compensating sheet according to a second embodiment of the present invention. In the embodiment shown in fig. 2 (a) and 2 (b), the composite lithium supplementing sheet includes a first lithium-containing metal body 1, a first membrane 2, and a second membrane 3. The first lithium-containing metal body 1 is of 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, the pore diameter of the micropores is 100 mu m, and the porosity of the through holes is 80%. The first membrane 2 and the second membrane 3 are respectively located 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 part 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 diaphragms at the two sides is a slow-release lithium supplementing area H, and the peripheral edge part of the first lithium-containing metal body 1 which is not covered by the diaphragms at the two sides is a first-effect lithium supplementing area S. The area ratio of the first-effect lithium supplementing region S to the slow-release lithium supplementing region H is 1/2.
Fig. 3 (a) and 3 (b) are an exploded view and a combined view of a composite lithium-compensating sheet according to a third embodiment of the present invention. In the embodiment shown in fig. 3 (a) and 3 (b), the composite lithium supplementing sheet includes a first lithium-containing metal body 1, a first substrate 4, a first membrane 2, and a second membrane 3. The first lithium-containing metal body 1 is in a separating sheet structure, a plurality of strip-shaped separating sheets are fixedly connected to the first substrate 4 from two sides of the first substrate 4 in a symmetrical mode, and the first substrate 4 is made of a composite of polypropylene and carbon black. The first membrane 2 and the second membrane 3 are made of a mixture of polypropylene and aluminum powder, micropores are formed in the first membrane 2 and the second membrane 3, the pore diameter of the micropores is 1000 mu m, and the porosity of the through holes is 50%. The first membrane 2 and the second membrane 3 are respectively located at both sides of the first substrate 4 provided with 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 and the first substrate 4, portions of the upper and lower edges 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 diaphragms at the two sides is a slow-release lithium supplementing area H, and the upper and lower edge parts of the first lithium-containing metal body 1 which are not covered by the diaphragms at the two sides are first effective lithium supplementing areas S. The area ratio of the first-effect lithium supplementing region S to the slow-release lithium supplementing region H is 1/4.
Fig. 4 (a) and 4 (b) are an exploded view and a combined view of a composite lithium-compensating sheet according to a fourth embodiment of the present invention. In the embodiment shown in fig. 4 (a) and 4 (b), the composite lithium supplementing sheet includes a first lithium-containing metal body 1, a first membrane 2, and a second membrane 3. The first lithium-containing metal body 1 is of a one-piece structure, and the conductive portion 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 the micropores is 1500 mu m, and the porosity of the through holes is 10%. 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 round openings 6 are respectively arranged on the first membrane 2 and the second membrane 3, the shape and the position of the opening of the first membrane 2 correspond to those of the opening of the second membrane 3, and the plurality of 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, 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 diaphragms at the two sides is a slow-release lithium supplementing region H, and the part of the first lithium-containing metal body 1 not covered by the diaphragms at the two sides is a first effective lithium supplementing region S. The area ratio of the first-effect lithium supplementing region S to the slow-release lithium supplementing region H is 1/5. The quantity of lithium supplement during first-effect lithium supplement can be controlled through the number and the size of the openings 6 on the membrane, and the uniformity of the first-effect lithium supplement and the lithium supplement 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 a combined view of a composite lithium-compensating sheet according to a fifth embodiment of the present invention. In the embodiment shown in fig. 5 (a) and 5 (b), the composite lithium supplementing sheet includes a first lithium-containing metal body 1, a first substrate 4, a first membrane 2, and a second membrane 3. The first lithium-containing metal body 1 is in a separating sheet structure, a plurality of strip-shaped separating 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 nano tubes, micropores are formed in the first membrane 2 and the second membrane 3, the pore diameter of the micropores is 20 mu m, and the porosity of the through holes 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 shape and the position of the opening of the first membrane 2 correspond to those of the opening of the second membrane 3, the position of the opening 6 is positioned on the strip-shaped first lithium-containing metal body 1, and the plurality of 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, the portion of the upper side of the first lithium-containing metal body 1 and the portion corresponding to the opening 6 are not covered. The part of the first lithium-containing metal body 1 covered by the diaphragms at the two sides is a slow-release lithium supplementing region H, and the part of the first lithium-containing metal body 1 not covered by the diaphragms at the two sides is a first effective lithium supplementing region S. The area ratio of the first-effect lithium supplementing region S to the slow-release lithium supplementing region H is 1/3.
Fig. 6 (a) and 6 (b) are an exploded view and a combined view of a composite lithium-compensating sheet according to a sixth embodiment of the present invention. In the embodiment shown in fig. 6 (a) and 6 (b), the composite lithium supplementing 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 of 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 the micropores is 400 mu m, and the porosity of the through holes 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 arranged on the second lithium-containing metal body 7, and the positions of the 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 at two sides is a slow-release lithium supplementing region H, and the second lithium-containing metal body 7 not covered by the diaphragms is a first-effect lithium supplementing region S. During the first effect lithium replenishment, the second lithium-containing metal body 7 is substantially completely consumed, and during the subsequent lithium replenishment, the first lithium-containing metal body 1 is slowly released through the micropores of the membrane. The area ratio of the first-effect lithium supplementing region S to the slow-release lithium supplementing region H is 1/2. The quantity of lithium supplement during first-effect lithium supplement can be controlled through the number and the size of the through holes 8 on the second lithium-containing metal body 7, and the uniformity degree during first-effect lithium supplement 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-compensating sheet according to a seventh embodiment of the present invention. In the embodiment shown in fig. 7 (a) and 7 (b), the composite lithium supplementing 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 of a monolithic structure. The first membrane 2 and the second membrane 3 are made of a mixture of polyethylene terephthalate and graphene, and micropores are formed in the first membrane 2 and the second membrane 3, the pore diameter of the micropores is 800 mu m, and the porosity of the through holes 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 of the plurality of separation sheet structures are fixedly connected to the second substrate 9, the 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 on the outer sides of the first membrane 2 and the second membrane 3. The second substrate 9 is a porous structure. The whole first lithium-containing metal body 1 covered by the diaphragms at two sides and the second substrate is a slow-release lithium supplementing region H, and the second lithium-containing metal body 7 not covered by the diaphragms is a first-effect lithium supplementing region S. During the first effect lithium replenishment, the second lithium-containing metal body 7 is substantially completely consumed, and during the subsequent lithium replenishment, the first lithium-containing metal body 1 is slowly released through the micropores of the membrane and the pores of the second substrate 9. The area ratio of the first-effect lithium supplementing region S to the slow-release lithium supplementing region H is 1/4. The number and the size of the separation sheets of the second lithium-containing metal body 7 can control the lithium supplementing amount during first-effect lithium supplementing, and the distribution position of the separation sheets can control the uniformity degree during first-effect lithium supplementing.
Fig. 8 (a) and 8 (b) are an exploded view and a combined view of a composite lithium-compensating sheet according to an eighth embodiment of the present invention. In the embodiment shown in fig. 8 (a) and 8 (b), the composite lithium supplementing 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 of a monolithic structure. The first membrane 2 and the second membrane 3 are made of a mixture of polysiloxane and carbon nano tubes, micropores are formed in the first membrane 2 and the second membrane 3, the pore diameter of the micropores is 2000 mu m, and the porosity of the through holes 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 of two curved strip structures are respectively positioned outside the first membrane 2 and the second membrane 3, and the curves are uniformly distributed in the whole area of the electrode plate. The whole first lithium-containing metal body 1 covered by the diaphragms at two sides is a slow-release lithium supplementing region H, and the second lithium-containing metal body 7 not covered by the diaphragms is a first-effect lithium supplementing region S. During the first effect lithium replenishment, the second lithium-containing metal body 7 is substantially completely consumed, and during the subsequent lithium replenishment, the first lithium-containing metal body 1 is slowly released through the micropores of the membrane. The area ratio of the first-effect lithium supplementing region S to the slow-release lithium supplementing region H is 1/3. The degree of uniformity in the first-effect lithium replenishment can be controlled by the uniformly distributed curve shape of the second lithium-containing metal body 7.
Fig. 9 is a partially exploded schematic view of a battery cell according to a first embodiment of the present invention. The battery cell comprises a positive electrode plate 10, a negative electrode plate 11, an isolating layer 12 and composite lithium supplementing plates 13a and 13b. Positive electrode sheet 10 and negative electrode sheet 11 are stacked alternately, and separator 12 is provided between positive electrode sheet 10 and negative electrode sheet 11. The positive electrode active material layer and the positive electrode current collector of the positive electrode sheet 10 adopt a porous structure, and the negative electrode active material layer and the negative electrode current collector of the negative electrode sheet 11 adopt a porous structure. In this embodiment, a composite lithium supplementing sheet is provided in each positive electrode sheet 10. In the adjacent two positive electrode sheets 10, a first composite lithium supplementing sheet 13a and a second composite lithium supplementing sheet 13b may be provided, respectively. The first composite lithium-supplementing sheet 13a and the second composite lithium-supplementing 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 positioned on two sides of the first lithium-containing metal body. In the first composite lithium-supplementing sheet 13a, the first lithium-containing metal body 1a is of a monolithic structure, a plurality of elongated openings are formed in the first membrane 2a and the second membrane 3a, the part covered by the first membrane 2a and the second membrane 3a forms a slow-release lithium-supplementing region 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 region 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 of a monolithic structure, a plurality of elongated openings are formed in the first membrane 2b and the second membrane 3b, the part covered by the first membrane 2b and the second membrane 3b forms a slow-release lithium-supplementing region 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 region S2 of the second composite lithium-supplementing sheet 13b. The long-strip-shaped slow release lithium supplementing region H1 of the first composite lithium supplementing sheet 13a and the long-strip-shaped slow release lithium supplementing region H2 of the second composite lithium supplementing sheet 13b are staggered, and the long-strip-shaped first-effect lithium supplementing region S1 of the first composite lithium supplementing sheet 13a and the long-strip-shaped first-effect lithium supplementing region S2 of the second composite lithium supplementing sheet 13b are staggered. For each positive plate, direct lithium supplement through adjacent composite lithium supplement plates and long-distance lithium supplement through a porous structure of a far-distance composite lithium supplement plate can realize more uniform lithium supplement on the whole surface of the positive plate no matter in the first-effect lithium supplement process or the long-term lithium supplement process.
Fig. 10 is a partially exploded view of a battery cell according to a second embodiment of the present invention. The battery cell comprises a positive electrode plate 10, a negative electrode plate 11, an isolating layer 12 and composite lithium supplementing plates 13a and 13b. Positive electrode sheet 10 and negative electrode sheet 11 are stacked alternately, and separator 12 is provided between positive electrode sheet 10 and negative electrode sheet 11. The positive electrode active material layer and the positive electrode current collector of the positive electrode sheet 10 adopt a porous structure, and the negative electrode active material layer and the negative electrode current collector of the negative electrode sheet 11 adopt a porous structure. In this embodiment, one or more positive electrode sheets not provided with the composite lithium supplementing sheet are spaced between two positive electrode sheets provided with the composite lithium supplementing sheet. In the adjacent two positive electrode sheets 10 provided with the composite lithium supplementing sheets, a first composite lithium supplementing sheet 13a and a second composite lithium supplementing sheet 13b may be provided, respectively. The first composite lithium-supplementing sheet 13a and the second composite lithium-supplementing 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 diaphragm and the second diaphragm 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 separation sheets, the plurality of separation 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 region 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 region 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 separation sheets, the plurality of separation 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 region 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 region S2 of the second composite lithium-supplementing sheet 13b. The first effective lithium supplementing region S1 of the first composite lithium supplementing sheet 13a and the first effective lithium supplementing region S2 of the second composite lithium supplementing sheet 13b are staggered with each other at the transverse position of the separation sheet and at the uncovered part. For each positive plate, the direct lithium supplement of the adjacent composite lithium supplement plates and the remote lithium supplement of the distant composite lithium supplement plates penetrating through the porous structure can realize more uniform lithium supplement on the whole surface of the positive plate.
The embodiments of the present invention are not intended to limit the present invention. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or modifications to equivalent embodiments using the methods and technical contents disclosed above, without departing from the scope of the technical solution of the present invention. Therefore, any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention still fall within the scope of the technical solution of the present invention.
Claims (14)
1. The composite lithium supplementing sheet is characterized by comprising a first diaphragm, a second diaphragm and a first lithium-containing metal body, wherein the first diaphragm and the second diaphragm are symmetrical in structure, the first diaphragm and the second diaphragm are arranged on two sides of the first lithium-containing metal body, the first diaphragm and the second diaphragm 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 diaphragm and the second diaphragm 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 diaphragm and the second diaphragm are provided with micropores, the pore diameter of the micropores is 0.01-2000 mu m, the through hole porosity of the micropores is 10-90%, and the area ratio of the first-effect lithium supplementing area to the slow-release lithium supplementing 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 is symmetrical to the structure of the 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 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 area of the second lithium-containing metal body and the area of 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 effective 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 pore porosity of the micropores is 10-90%, and the ratio of the first effective lithium supplementing area to the slow release lithium supplementing area is 1/2.
2. The composite lithium-compensating sheet of claim 1, wherein the first lithium-containing metal body is of monolithic construction; alternatively, the first lithium-containing metal body is a plurality of separator structures, and the plurality of separators are partially connected or spaced apart from each other.
3. The composite lithium-supplementing sheet according to claim 1 or 2, wherein an opening is provided on the first and second diaphragms, the opening is curved, and the openings are uniformly distributed on the first and second diaphragms; or a plurality of openings are formed in the first membrane and the second membrane, the openings are circular, elliptical, curved or polygonal, and the openings are uniformly distributed in the first membrane and the second membrane.
4. The composite lithium-compensating sheet of claim 1 or 2, wherein the composite lithium-compensating sheet further comprises a first substrate, the first lithium-containing metal body being fixedly attached to the first substrate.
5. The composite lithium supplementing tablet according to claim 1 or 2, wherein the second lithium-containing metal body is of a monolithic structure, a through hole is formed in the second lithium-containing metal body, the through hole is of a curve shape, and the through holes are uniformly distributed in the second lithium-containing metal body; or, a plurality of through holes are formed in the second lithium-containing metal body, the through holes are circular, elliptical, curved or polygonal in shape, and the through holes are uniformly distributed in the second lithium-containing metal body.
6. The composite lithium-compensating sheet of claim 1 or 2, wherein the second lithium-containing metal body is a plurality of separator structures, the plurality of separator structures being partially connected or spaced apart from each other.
7. The composite lithium-compensating sheet of claim 1 or 2, wherein the second lithium-containing metal body is a long strip structure having a uniformly distributed curved shape.
8. The composite lithium-compensating sheet of claim 1 or 2, wherein the composite lithium-compensating sheet further comprises a second substrate, the second lithium-containing metal body being fixedly attached to the second substrate, the second substrate being of porous structure.
9. The composite lithium-compensating sheet of claim 1 or 2, wherein the first and second membranes are polymeric conductive layers of a material that is a composite or mixture of a polymer and a conductive material, the polymer being polyethylene, polypropylene, polyethylene-propylene copolymer, polytetrafluoroethylene, polyethylene terephthalate, polypyrrole, polyvinylidene fluoride-hexafluoropropylene copolymer, polymethyl methacrylate, polyethylene oxide, aliphatic polycarbonate, or polysiloxane, the conductive material being a conductive carbon material or a conductive metal material.
10. The composite lithium-supplementing sheet according to claim 1 or 2, wherein the first and second membranes are insulating layers, the insulating layers are made of a polymer or a composite of a polymer and an inorganic nonmetallic material, the polymer is polyethylene, polypropylene, a polyethylene-propylene copolymer or polytetrafluoroethylene, the inorganic nonmetallic material is alumina or silica, and the composite lithium-supplementing sheet further comprises a conductive part which electrically connects the sustained-release lithium-supplementing region of the composite lithium-supplementing sheet with the positive electrode tab of the battery or with the negative electrode tab of the battery.
11. A battery cell of a battery, characterized in that the battery cell comprises a positive plate, a negative plate, an isolation layer and a composite lithium supplementing plate according to any one of claims 1 to 10, wherein the positive plate and the negative plate are alternately laminated, the isolation layer is arranged between the positive plate and the negative plate, and the composite lithium supplementing plate is arranged inside the positive plate or between the positive plate and the isolation layer; or, the composite lithium supplementing sheet is arranged in the negative electrode sheet or between the negative electrode sheet and the isolating layer.
12. The cell of claim 11, wherein the positions of the sustained release lithium-compensating regions of adjacent two composite lithium-compensating tablets are staggered with respect to each other.
13. The cell of claim 11 or 12, wherein the locations of the first effective lithium replenishment regions of adjacent two composite lithium replenishment sheets are staggered with respect to each other.
14. A battery comprising a housing and a cell as claimed in any one of claims 11 to 13.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200412686A (en) * | 2003-01-06 | 2004-07-16 | Hon Hai Prec Ind Co Ltd | Lithium ion battery |
| JP2005109199A (en) * | 2003-09-30 | 2005-04-21 | Kanebo Ltd | Film type electric storage device |
| CN105932206A (en) * | 2016-07-13 | 2016-09-07 | 洛阳力容新能源科技有限公司 | Lithium supplement composite diaphragm, preparation method and application |
| CN106684291A (en) * | 2016-12-29 | 2017-05-17 | 深圳天珑无线科技有限公司 | Lithium ion battery and preparation method thereof |
| CN107681115A (en) * | 2016-08-01 | 2018-02-09 | 北京好风光储能技术有限公司 | A kind of negative plate of lithium slurry battery |
| CN107845829A (en) * | 2017-10-12 | 2018-03-27 | 北京卫蓝新能源科技有限公司 | A kind of two-layer compound diaphragm cell and its benefit lithium method |
| CN108242530A (en) * | 2016-12-23 | 2018-07-03 | 北京好风光储能技术有限公司 | A kind of lithium slurry battery and its negative plate |
| CN109461885A (en) * | 2018-10-12 | 2019-03-12 | 惠州亿纬锂能股份有限公司 | Lithium ion battery with high energy density |
| CN109786662A (en) * | 2019-01-18 | 2019-05-21 | 湖北锂诺新能源科技有限公司 | A kind of negative electrode of lithium ion battery mends pole piece and preparation method thereof |
| CN109817473A (en) * | 2018-12-13 | 2019-05-28 | 中国科学院电工研究所 | A kind of pre-embedding lithium method of lithium ion electrochemical energy storage device |
| CN209071480U (en) * | 2018-12-12 | 2019-07-05 | 中能中科（天津）新能源科技有限公司 | Diaphragm containing lithium, lithium battery electric core, lithium battery |
| CN110729451A (en) * | 2018-07-17 | 2020-01-24 | 惠州比亚迪电池有限公司 | Positive plate and preparation method thereof, lithium ion battery and vehicle |
| CN111446489A (en) * | 2020-05-07 | 2020-07-24 | 浙江浙能技术研究院有限公司 | Lithium ion battery structure and lithium supplementing method |
| CN111519135A (en) * | 2020-03-30 | 2020-08-11 | 维达力实业(深圳)有限公司 | Shielding device and lithium supplementing equipment |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10593952B2 (en) * | 2015-05-19 | 2020-03-17 | 24M Technologies Inc. | Mechanical systems and methods for providing edge support and protection in semi-solid electrodes |
-
2020
- 2020-09-27 CN CN202011030722.3A patent/CN114284463B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW200412686A (en) * | 2003-01-06 | 2004-07-16 | Hon Hai Prec Ind Co Ltd | Lithium ion battery |
| JP2005109199A (en) * | 2003-09-30 | 2005-04-21 | Kanebo Ltd | Film type electric storage device |
| CN105932206A (en) * | 2016-07-13 | 2016-09-07 | 洛阳力容新能源科技有限公司 | Lithium supplement composite diaphragm, preparation method and application |
| CN107681115A (en) * | 2016-08-01 | 2018-02-09 | 北京好风光储能技术有限公司 | A kind of negative plate of lithium slurry battery |
| CN108242530A (en) * | 2016-12-23 | 2018-07-03 | 北京好风光储能技术有限公司 | A kind of lithium slurry battery and its negative plate |
| CN106684291A (en) * | 2016-12-29 | 2017-05-17 | 深圳天珑无线科技有限公司 | Lithium ion battery and preparation method thereof |
| CN107845829A (en) * | 2017-10-12 | 2018-03-27 | 北京卫蓝新能源科技有限公司 | A kind of two-layer compound diaphragm cell and its benefit lithium method |
| CN110729451A (en) * | 2018-07-17 | 2020-01-24 | 惠州比亚迪电池有限公司 | Positive plate and preparation method thereof, lithium ion battery and vehicle |
| CN109461885A (en) * | 2018-10-12 | 2019-03-12 | 惠州亿纬锂能股份有限公司 | Lithium ion battery with high energy density |
| CN209071480U (en) * | 2018-12-12 | 2019-07-05 | 中能中科（天津）新能源科技有限公司 | Diaphragm containing lithium, lithium battery electric core, lithium battery |
| CN109817473A (en) * | 2018-12-13 | 2019-05-28 | 中国科学院电工研究所 | A kind of pre-embedding lithium method of lithium ion electrochemical energy storage device |
| CN109786662A (en) * | 2019-01-18 | 2019-05-21 | 湖北锂诺新能源科技有限公司 | A kind of negative electrode of lithium ion battery mends pole piece and preparation method thereof |
| CN111519135A (en) * | 2020-03-30 | 2020-08-11 | 维达力实业(深圳)有限公司 | Shielding device and lithium supplementing equipment |
| CN111446489A (en) * | 2020-05-07 | 2020-07-24 | 浙江浙能技术研究院有限公司 | Lithium ion battery structure and lithium supplementing method |
Non-Patent Citations (2)
| Title |
|---|
| 刘丹丹 等.《化学进展》锂浆料电池基础科学问题研究.2018,第30卷(第6期),第765-774页. * |
| 操建华 等.《中国科学:化学》锂电隔膜研究及产业技术进展.2014,第44卷(第7期),第1125-1149页. * |
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