CN114583143A - Negative electrode lithium-supplementing lithium tape and preparation method and application thereof - Google Patents
Negative electrode lithium-supplementing lithium tape and preparation method and application thereof Download PDFInfo
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- CN114583143A CN114583143A CN202210224673.XA CN202210224673A CN114583143A CN 114583143 A CN114583143 A CN 114583143A CN 202210224673 A CN202210224673 A CN 202210224673A CN 114583143 A CN114583143 A CN 114583143A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 322
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 321
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000013589 supplement Substances 0.000 claims abstract description 114
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 238000005096 rolling process Methods 0.000 claims description 31
- 239000007773 negative electrode material Substances 0.000 claims description 27
- 238000003490 calendering Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 17
- 230000001502 supplementing effect Effects 0.000 claims description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 238000009830 intercalation Methods 0.000 claims description 6
- 230000002687 intercalation Effects 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 241000251468 Actinopterygii Species 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 238000003780 insertion Methods 0.000 claims description 2
- 230000037431 insertion Effects 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 11
- 238000009792 diffusion process Methods 0.000 abstract description 10
- 230000008595 infiltration Effects 0.000 abstract description 10
- 238000001764 infiltration Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000010410 layer Substances 0.000 description 54
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 31
- 239000010439 graphite Substances 0.000 description 31
- 229910002804 graphite Inorganic materials 0.000 description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000011889 copper foil Substances 0.000 description 10
- 239000011888 foil Substances 0.000 description 9
- 239000002131 composite material Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 4
- 238000013329 compounding Methods 0.000 description 4
- 239000011267 electrode slurry Substances 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000009469 supplementation Effects 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000003014 reinforcing effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005489 elastic deformation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000009191 jumping Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- 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 negative lithium supplement lithium tape and a preparation method and application thereof. The thickness of the negative electrode lithium supplement lithium strip is 3-10 mu m, and at least one region is arranged on the surface of the negative electrode lithium supplement lithium strip. According to the invention, the areas are arranged in the negative electrode lithium supplement lithium belt, the criss-cross heat diffusion and electrolyte infiltration network is formed in the areas, the gas production problem caused by poor or slow electrode sheet infiltration after the negative electrode sheet is covered by the lithium belt is solved, the dissolving efficiency of metal lithium in the negative electrode is improved, and the lithium supplement effect of the negative electrode is effectively improved. Meanwhile, the thickness of the lithium belt can be increased under the same lithium supplement amount, the lithium belt-pole piece combination efficiency is improved, and the lithium supplement precision of the battery is also improved.
Description
Technical Field
The invention belongs to the technical field of negative electrode lithium supplement, and relates to a negative electrode lithium supplement lithium belt and a preparation method and application thereof.
Background
At present, metal lithium foil is compounded on a negative pole piece mainly for lithium supplement of a negative pole, the metal lithium foil is made of relatively more ultrathin sheet lithium and strip-shaped lithium strips, the problem of over supplement of negative active lithium is solved by the metal lithium foil, the problem of wettability of the pole piece after lithium compounding is solved by the metal lithium, and the problem of low lithium calendering efficiency exists in the metal lithium.
CN105489846A discloses a method and a system for lithium supplement of a pole piece. The method comprises compounding a first substrate and a first lithium tape to form a first lithium composite tape, and forming a barrier between the first lithium tape and the compounding device by using a second substrate; compounding the first composite lithium belt and the lithium pole piece to be compensated to form a lithium compensation composite pole piece, wherein the first base material is positioned on one side far away from the lithium pole piece to be compensated in the process; and stripping and rolling the first substrate to form a lithium supplement pole piece. The device comprises a pole piece unreeling device, a first composite lithium belt conveying device, a pole piece lithium supplementing rolling device, a first pole piece stripping device and a first substrate reeling device, wherein the pole piece lithium supplementing rolling device comprises two oppositely arranged press rollers. The process is complex, the precision is difficult to control, and the following problems also exist: 1) the multiple base bands are required to be wound and unwound, the base bands are pressed and delayed by a rolling roller, and the base bands are stressed, deformed and wrinkled due to the inconsistent elastic deformation; 2) the thickness deviation of the base band is existed, so that the thickness tolerance of the rolled lithium foil is indirectly expanded; 3) the cost of the baseband itself is also high; 4) the requirement for lithium belt materials is high.
CN109728306A discloses a lithium-supplementing negative electrode plate and a preparation method thereof, wherein the lithium-supplementing negative electrode plate includes a negative electrode current collector, a first negative electrode slurry layer disposed on two surfaces of the negative electrode current collector, a lithium foil layer closely attached to the surface of the first negative electrode slurry layer, and a second negative electrode slurry layer disposed on the surface of the lithium foil layer. Compared with the prior art, the invention realizes the effect of lithium supplement on the negative plate, improves the first efficiency and the cycle performance of the battery, and simultaneously adds the second negative slurry layer on the surface of the lithium foil layer, thereby avoiding the lithium foil layer from being exposed in the air and reducing the requirement of production conditions. However, the lithium foil layer in the document is easily oxidized when being contacted with moisture in the slurry during the coating process of the second negative electrode slurry, and the lithium-supplement negative electrode sheet has the risk of falling after being compounded.
Therefore, how to supplement lithium by using a lithium band to improve the lithium supplementing effect of the negative electrode is a technical problem to be solved urgently.
Disclosure of Invention
The invention aims to provide a negative lithium supplement lithium tape and a preparation method and application thereof. According to the invention, the areas are arranged in the negative electrode lithium supplement lithium belt, the criss-cross heat diffusion and electrolyte infiltration network is formed in the areas, the gas production problem caused by poor or slow electrode sheet infiltration after the negative electrode sheet is covered by the lithium belt is solved, the dissolving efficiency of metal lithium in the negative electrode is improved, and the lithium supplement effect of the negative electrode is effectively improved. Meanwhile, the thickness of the lithium belt can be increased under the same lithium supplement amount, the lithium belt-pole piece combination efficiency is improved, and the lithium supplement precision of the battery is also improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a negative electrode lithium supplement lithium strip, the thickness of the negative electrode lithium supplement lithium strip is 3-10 μm, and at least one region is arranged on the surface of the negative electrode lithium supplement lithium strip.
In the negative electrode lithium-supplement lithium belt provided by the invention, the region aims to form a criss-cross heat diffusion and electrolyte infiltration network, the problem of gas production caused by poor or slow electrode sheet infiltration after the negative electrode sheet is covered by the lithium belt is solved, the dissolving efficiency of metal lithium in the negative electrode is improved, and the lithium-supplement effect of the negative electrode is effectively improved. Meanwhile, the thickness of the lithium belt can be increased under the same lithium supplement amount, the lithium belt-pole piece combination efficiency is improved, and the lithium supplement precision of the battery is also improved. And the arrangement of the regions can play a role of reinforcing ribs in the lithium belt, so that the strength of the lithium-clad pole piece is further improved.
Preferably, the shape of the region includes any one of a rectangular shape, a square shape, a circular shape, an elliptical shape, a fingerprint shape, an island shape, or a fish scale shape, or a combination of at least two thereof.
In the present invention, the shape of the region may be a regular shape or an irregular shape.
Preferably, the regions are distributed on the surface of the negative electrode lithium supplement lithium belt in a continuous state or a discontinuous state.
Preferably, the area has a maximum length of 100 μm to 500mm, for example a maximum length of 100 μm, 300 μm, 500 μm, 800 μm, 1000 μm, 100mm, 200mm, 300mm, 400mm or 500mm, etc., and a maximum width of 50 to 3000 μm, for example a maximum width of 50 μm, 100 μm, 300 μm, 500 μm, 800 μm, 1000 μm, 1300 μm, 1500 μm, 1800 μm, 2000 μm, 2300 μm, 2500 μm, 2800 μm or 3000 μm, etc.
In the invention, the area in the lithium strip structure must be limited, and the width is too wide or the length is too long, which is not beneficial to heat diffusion, on the contrary, the thickness of the lithium strip is increased under the same lithium supplement amount, and the capacity of the aluminum shell battery cell is reduced.
Preferably, when the regions are distributed in a discontinuous state, the interval between each region is 10-1000 μm, such as 10 μm, 50 μm, 100 μm, 200 μm, 300 μm, 400 μm, 500 μm, 600 μm, 700 μm, 800 μm, 900 μm or 1000 μm.
Preferably, the negative lithium-supplemented lithium band is doped with a non-lithium element comprising any one or a combination of at least two of Al, Sn, Si or Mg.
Preferably, the mass of the non-lithium element is 0.01 to 2% of the mass of the negative electrode lithium-complementary lithium strip, for example, 0.01, 0.05%, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.3%, 1.5%, 1.8%, or 2%.
In the invention, the lithium ribbon becomes brittle and is easy to break due to excessive non-lithium elements.
In a second aspect, the present invention provides a method for preparing a negative lithium-supplemented lithium strip according to the first aspect, the method comprising the following steps:
(1) mixing molten metal lithium and non-lithium elements, and pressing to obtain an initial lithium belt;
(2) and (2) carrying out calendering treatment on the initial lithium strip obtained in the step (1) to enable the rolling linear speed ratio of the fast and slow rollers to be 1-50%, so as to obtain the negative electrode lithium supplement lithium strip.
For example, the ratio of the roll surface linear velocities of the fast and slow rolls may be 1%, 3%, 4%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, or the like.
Compared with pure metal lithium, the composite metal lithium has stronger strength, and an area is easy to form under the combined action of factors such as strong extrusion force, strong tensile force, roll rhythmicity jumping and the like in the rapid rolling process.
The speed provided by the invention refers to the relative speed of the rolling speed between the upper roller and the lower roller in the rolling process.
The ratio of the roller surface line speeds of the fast roller and the slow roller provided by the invention is the ratio of the roller surface line speeds of the fast roller and the slow roller, and the result is obtained.
When the negative electrode lithium-supplement lithium strip is prepared, the speed ratio of the fast and slow rollers is adjusted in the process of carrying out secondary rolling on the initial lithium strip, so that the rolling surface line speeds of the fast and slow rollers during rolling are different, and the lithium-supplement lithium strip with the surface area in the tiled arrangement can be obtained in the rolling process.
In the invention, if the rolling linear speed of the fast and slow rollers is kept consistent, an ultrathin lithium belt with a region on the surface cannot be obtained, and the thickness of the lithium belt is thicker.
Preferably, the thickness of the initial lithium ribbon in step (1) is 30 μm to 30mm, such as 30 μm, 50 μm, 100 μm, 500 μm, 1mm, 2mm, 3mm, 4mm, 5mm, 10mm, 15mm, 20mm, 25mm, or 30mm, and preferably 50 μm to 5 mm.
Preferably, the width of the initial lithium tape in the step (1) is 10-1000 mm, such as 10mm, 20mm, 50mm, 100mm, 150mm, 200mm, 250mm, 300mm, 400mm, 500mm, 700mm or 1000 mm.
Preferably, the pressure of the rolling treatment in the step (2) is 1 to 5T, such as 1T, 1.5T, 2T, 2.5T, 3T, 3.5T, 4T, 4.5T or 5T, and the like, and preferably 1 to 3T.
In the calendering process, when the pressure is 1-3T, the lithium belt is more favorable for forming the lithium belt which is flatly arranged in the area of the surface of the lithium belt, so that the thickness of the lithium belt is more uniform, the gap is more uniform, and the stripping of the release film is more favorable
Preferably, in the rolling treatment in the step (2), the roller pitch is 40 to 110 μm, such as 40 μm, 50 μm, 55 μm, 60 μm, 65 μm, 70 μm, 75 μm, 80 μm, 85 μm, 90 μm, 95 μm, 100 μm, 105 μm or 110 μm, and preferably 50 to 80 μm.
In the invention, the roller spacing refers to the minimum surface spacing of the fast and slow rollers, and when the surface spacing is within the range of 50-80 mu m, the formation of lithium strips with areas on the surface with uniform thickness is facilitated.
Preferably, the rolling linear speed ratio of the fast and slow rollers in the step (2) is 2-30%, such as 2%, 3%, 5%, 10%, 15%, 20%, 25%, or 30%.
In the invention, the rolling linear speed ratio of the fast and slow rollers in the step (2) is within the range of 2-30%, and the method is more favorable for preparing the lithium belt with the thickness of 3-10 mu m.
Preferably, in the rolling treatment in step (2), the rolling speed is 5-100 m/min, such as 5m/min, 10m/min, 20m/min, 30m/min, 40m/min, 50m/min, 60m/min, 70m/min, 80m/min, 90m/min or 100m/min, and preferably 20-100 m/min.
According to the invention, the lithium-supplement lithium belts with the surfaces in the region-tiled arrangement are prepared, the calendering speed is not particularly strictly limited, and the efficiency of calendering and laminating the lithium belts and the negative pole piece is favorably improved after the calendering speed is increased to 20 m/min.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) mixing molten metal lithium and non-lithium elements, and pressing to obtain an initial lithium belt with the width of 10-1000 mm and the thickness of 50 mu m-5 mm;
(2) and (2) conveying the initial lithium strip obtained in the step (1), and then performing calendering treatment at a calendering speed of 20-100 m/min by adopting a pressure of 1-3T, wherein the distance between rollers is kept to be 50-80 mu m, and the ratio of the rolling linear speeds of a fast roller and a slow roller is 2-30%, so as to obtain the negative electrode lithium supplement lithium strip.
In a third aspect, the present invention provides a negative lithium supplementation pole piece, which includes a negative current collector, a negative active material layer disposed on at least one surface of the negative current collector, and at least one negative lithium supplementation lithium strip as described in the first aspect disposed on the surface of the negative active material layer away from the current collector.
Preferably, the mass of the negative electrode lithium-supplemented lithium ribbon is 0.1 to 2% of the mass of the negative electrode active material layer, for example, 0.1%, 0.3%, 0.5%, 0.8%, 1%, 1.3%, 1.5%, 1.8%, 2%, or the like, preferably 0.5 to 1.5%.
According to the invention, the mass of the negative electrode lithium supplement lithium band is less than 0.1%, on one hand, the lithium supplement amount is insufficient, so that the battery capacity is reduced, and on the other hand, the amount of the lithium supplement lithium band cannot be controlled, so that the precision is low, and the battery consistency is poor.
Preferably, an angle formed by the tangential direction of any point in the negative electrode lithium supplementing strip and the length direction of the negative electrode lithium supplementing pole piece is 30-150 degrees, such as 30 degrees, 40 degrees, 50 degrees, 60 degrees, 70 degrees, 80 degrees, 90 degrees, 100 degrees, 110 degrees, 120 degrees, 130 degrees, 140 degrees or 150 degrees.
In the invention, the angle formed by the tangential direction of any point in the negative electrode lithium supplementing strip and the length direction of the negative electrode lithium supplementing pole piece is 30-150 degrees, and if the angle is not in the range, the pole piece powder falling or the lithium strip falling in the winding process can be caused.
Preferably, the negative electrode lithium-supplementing lithium strips cover the surface of the negative electrode active material coating layer to form covering areas, gaps between the negative electrode lithium-supplementing lithium strips form non-covering areas, and the width ratio of the covering areas to the non-covering areas along the length direction of the pole piece is 0.1-0.99, such as 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9 or 0.99, and the like, and preferably 0.2-0.8.
According to the invention, along the length direction of the pole piece, the ratio of the width of the coverage area to the width of the non-coverage area is less than 0.2, the lithium supplement amount is low, and the capacity is improved a little; the thermal diffusion is blocked more than 0.8, the temperature of the battery is overhigh, and the safety risk exists
Preferably, the length of the part, covered by the negative electrode active material layer, of the negative electrode lithium supplement lithium strip along the width direction of the negative electrode lithium supplement electrode sheet is A1, and the length of the part, uncovered by the negative electrode active material layer, of the negative electrode lithium supplement lithium strip is A0, wherein A1/A0 is more than 16, such as 17, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 250 or 300, and the like, and A1/A0 is 20-200.
Preferably, after the negative electrode lithium supplement electrode sheet is formed, the ratio S1/S0 of the sum S1 of the projection areas of the lithium supplement oxidation layers remained on the negative electrode lithium supplement lithium belt on the negative electrode active material layer to the area S0 of the negative electrode active material layer is 19.6-78.4%, such as 19.6%, 20%, 30%, 40%, 50%, 60%, 70%, 75% or 78.4%.
Preferably, a part of lithium in the negative electrode lithium-replenishing lithium band on the surface of the negative electrode active material layer forms a second lithium intercalation compound under the action of an electrolyte, the second lithium intercalation compound exists on the surface of the negative electrode active material layer, and the second lithium intercalation compound is in a discontinuous state of interval distribution on the surface of the negative electrode active material layer.
Preferably, the second lithium insertion compound is lithium oxide.
In a fourth aspect, the invention further provides a lithium ion battery, which includes the negative electrode lithium supplement electrode sheet according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) in the negative electrode lithium-supplement lithium belt provided by the invention, the region aims to form a criss-cross heat diffusion and electrolyte infiltration network, the problem of gas production caused by poor or slow electrode sheet infiltration after the negative electrode sheet is covered by the lithium belt is solved, the dissolving efficiency of metal lithium in the negative electrode is improved, and the lithium-supplement effect of the negative electrode is effectively improved. Meanwhile, the thickness of the lithium belt can be increased under the same lithium supplement amount, the lithium belt-pole piece combination efficiency is improved, and the lithium supplement precision of the battery is also improved. And the arrangement of the regions can play a role of reinforcing ribs in the lithium belt, so that the strength of the lithium-clad pole piece is further improved. The first effect under 1C of the battery obtained by applying the negative lithium-supplementing lithium belt provided by the invention to a negative pole piece can reach more than 95%, and the capacity retention rate after circulation for 2000 times can reach more than 96%.
(2) According to the invention, the speed ratio of the fast and slow rollers is adjusted in the calendering process, so that the linear speeds of the fast and slow rollers during rolling are different, and the lithium supplement lithium belt with the surface in a region-shaped tiled arrangement is obtained.
Drawings
Fig. 1 is a schematic view of a negative lithium-supplemented lithium tape provided in example 2.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
This example provides a negative lithium-supplemented lithium tape having the properties shown in table 1.
The preparation method of the negative lithium-supplement lithium strip comprises the following steps:
(1) mixing molten metal lithium with Al, and pressing to obtain an initial lithium belt with the width of 50mm and the thickness of 2 mm;
(2) and (2) conveying the initial lithium strip obtained in the step (1), and then carrying out calendering treatment at a calendering speed of 50m/min by adopting a pressure of 2.5T, wherein the roller spacing is kept at 60 mu m, and the ratio of the rolling linear speeds of the fast and slow rollers is 5%, so as to obtain the negative electrode lithium supplement strip.
Example 2
This example provides a negative lithium-supplemented lithium tape having the properties shown in table 1.
The remaining preparation methods and parameters were in accordance with example 1.
Fig. 1 shows a schematic diagram of a negative lithium-supplemented lithium strip provided in example 2, and as can be seen from fig. 1, the surface of the lithium strip is provided with a plurality of rectangular areas.
Example 3
This example provides a negative lithium-supplemented lithium tape having the properties shown in table 1.
The preparation method of the negative lithium-supplement lithium strip comprises the following steps:
(1) mixing molten metal lithium with Si, and pressing to obtain an initial lithium belt with the width of 200mm and the thickness of 5 mm;
(2) and (2) conveying the initial lithium strip obtained in the step (1), and then carrying out calendering treatment at a calendering speed of 80m/min by adopting a pressure of 1.5T, wherein the roller spacing is kept at 80 mu m, and the ratio of the rolling linear speeds of the fast and slow rollers is 30%, so as to obtain the negative electrode lithium supplement strip.
Example 4
This example provides a negative lithium-supplemented lithium tape having the properties shown in table 1.
(1) Mixing molten metal lithium with Si, and pressing to obtain an initial lithium belt with the width of 300mm and the thickness of 1 mm;
(2) and (2) conveying the initial lithium strip obtained in the step (1), and then carrying out calendering treatment at a calendering speed of 100m/min by adopting a pressure of 3T, wherein the roller spacing is kept at 70 mu m, and the ratio of the rolling linear speeds of the fast and slow rollers is 10%, so as to obtain the negative electrode lithium supplement strip.
Examples 5-10 provided negative lithium-supplemented lithium tapes having the properties shown in table 1.
The preparation process is referred to example 1.
The negative electrode lithium-supplemented lithium tapes provided in comparative examples 1-2 have the properties shown in table 1.
The preparation process is referred to example 1.
Comparative example 3
The comparative example differs from example 5 in that the negative electrode lithium-supplemented lithium strip provided in the comparative example is not provided with a region on the surface, and the properties thereof are also shown in table 1.
The difference between the preparation method and the example 1 is that the ratio of the rolling linear speeds of the fast and slow rollers is 0.1%, and the rest preparation method and parameters are consistent with the example 1.
TABLE 1
The negative lithium-supplemented lithium tapes provided in examples 1 to 10 and comparative examples 1 to 3 were applied to the surface of the active material layer of the negative electrode sheet, and the ratio of the lithium tapes was kept uniform.
Coiling graphite-based negative pole piece, lithium iron phosphate positive pole piece and non-woven fabric diaphragm to obtain an electric core, injecting carbonate electrolyte to obtain a lithium ion battery, and carrying out electrochemical performance test under the test conditions that: the results of the normal temperature cycle 1C charge, 1C discharge, and a charge window of 2.5 to 3.65V are shown in Table 2.
TABLE 2
From the data results of the embodiment 1 and the embodiment 2, it can be known that certain intervals exist between the regions, which is more beneficial to heat diffusion in the pre-lithium process, reduces the occurrence of side reactions caused by heat, improves the first effect, and improves the lithium supplement efficiency.
From the data results of example 5 and comparative example 1, it can be seen that the lithium-supplemented lithium band of the negative electrode is too thin, which results in insufficient thermal diffusion channel, reduced first-pass and lithium-supplementing efficiency, and reduced cycle life.
From the data results of example 6 and comparative example 2, it is known that the negative electrode lithium-supplemented lithium band is too thick, the gap is too large, the lithium compensation uniformity is insufficient, and in addition, the residual dead lithium is increased, and the first effect and the lithium supplementation efficiency are reduced.
From the data results of the example 5 and the comparative example 3, it can be seen that compared with the conventional lithium-supplement lithium tape, the lithium-supplement lithium tape provided by the invention is more beneficial to reducing the tape breakage frequency of the lithium tape and improving the production efficiency.
Application example 1
The application example provides a negative electrode lithium supplement pole piece, which comprises a copper foil, a graphite electrode layer arranged on the surface of a negative electrode current collector, and the negative electrode lithium supplement lithium strip provided in the embodiment 5, wherein the graphite electrode layer is arranged on the surface of the graphite electrode layer, which is far away from the surface of the current collector.
The ratio of the negative electrode lithium supplement lithium ribbon in the negative electrode lithium supplement electrode sheet and various position definitions are shown in table 3.
Application example 2
The application example provides a negative electrode lithium supplement pole piece, which comprises a copper foil, a graphite electrode layer arranged on the surface of a negative electrode current collector, and the negative electrode lithium supplement lithium strip provided in the embodiment 5, wherein the graphite electrode layer is arranged on the surface of the graphite electrode layer, which is far away from the surface of the current collector.
The ratio of the negative lithium-supplemented lithium bands in the negative lithium-supplemented electrode sheet and the various position definitions are shown in table 3.
Application example 3
The application example provides a negative electrode lithium supplement pole piece, which comprises a copper foil, a graphite electrode layer arranged on the surface of a negative electrode current collector, and the negative electrode lithium supplement lithium strip provided in the embodiment 6, wherein the graphite electrode layer is arranged on the surface of the graphite electrode layer, which is far away from the surface of the current collector.
The ratio of the negative lithium-supplemented lithium bands in the negative lithium-supplemented electrode sheet and the various position definitions are shown in table 3.
Application example 4
The application example provides a negative electrode lithium supplement pole piece, which comprises a copper foil, a graphite electrode layer arranged on the surface of a negative electrode current collector, and the negative electrode lithium supplement lithium strip provided in the embodiment 5, wherein the graphite electrode layer is arranged on the surface of the graphite electrode layer, which is far away from the surface of the current collector.
The ratio of the negative lithium-supplemented lithium bands in the negative lithium-supplemented electrode sheet and the various position definitions are shown in table 3.
Application example 5
The application example provides a negative electrode lithium supplement pole piece, which comprises a copper foil, a graphite electrode layer arranged on the surface of a negative electrode current collector, and the negative electrode lithium supplement lithium strip provided in the embodiment 6, wherein the graphite electrode layer is arranged on the surface of the graphite electrode layer, which is far away from the surface of the current collector.
The ratio of the negative lithium-supplemented lithium bands in the negative lithium-supplemented electrode sheet and the various position definitions are shown in table 3.
Application example 6
The application example provides a negative electrode lithium supplement pole piece, which comprises a copper foil, a graphite electrode layer arranged on the surface of a negative electrode current collector, and the negative electrode lithium supplement lithium strip provided in the embodiment 5, wherein the graphite electrode layer is arranged on the surface of the graphite electrode layer, which is far away from the surface of the current collector.
The ratio of the negative lithium-supplemented lithium bands in the negative lithium-supplemented electrode sheet and the various position definitions are shown in table 3.
Application example 7
The application example provides a negative electrode lithium supplement pole piece, which comprises a copper foil, a graphite electrode layer arranged on the surface of a negative electrode current collector, and the negative electrode lithium supplement lithium strip provided in the embodiment 5, wherein the graphite electrode layer is arranged on the surface of the graphite electrode layer, which is far away from the surface of the current collector.
The ratio of the negative lithium-supplemented lithium bands in the negative lithium-supplemented electrode sheet and the various position definitions are shown in table 3.
Application example 8
The application example provides a negative electrode lithium supplement pole piece, which comprises a copper foil, a graphite electrode layer arranged on the surface of a negative electrode current collector, and the negative electrode lithium supplement lithium strip provided in the embodiment 5, wherein the graphite electrode layer is arranged on the surface of the graphite electrode layer, which is far away from the surface of the current collector.
The ratio of the negative lithium-supplemented lithium bands in the negative lithium-supplemented electrode sheet and the various position definitions are shown in table 3.
Application example 9
The application example provides a negative electrode lithium supplement pole piece, which comprises a copper foil, a graphite electrode layer arranged on the surface of a negative electrode current collector, and the negative electrode lithium supplement lithium strip provided in the embodiment 5, wherein the graphite electrode layer is arranged on the surface of the graphite electrode layer, which is far away from the surface of the current collector.
The ratio of the negative lithium-supplemented lithium bands in the negative lithium-supplemented electrode sheet and the various position definitions are shown in table 3.
Application example 10
The application example provides a negative electrode lithium supplementing pole piece which comprises a copper foil, a graphite electrode layer arranged on the surface of a negative electrode current collector and a negative electrode lithium supplementing lithium strip which is arranged on the graphite electrode layer and is far away from the surface of the current collector and is provided in a comparative example 3.
The ratio of the negative lithium-supplemented lithium bands in the negative lithium-supplemented electrode sheet and the various position definitions are shown in table 3.
Table 3 shows the mass of the negative electrode lithium supplement ribbon as the ratio (M) of the mass of the negative electrode active material layer, the angle formed by the starting point-ending point connecting line in the width direction of the negative electrode lithium supplement ribbon and the length direction of the negative electrode lithium supplement sheet, the specific components of the negative electrode lithium supplement ribbon, the ratio S1/S0 of the sum S1 of the projection areas of the residual lithium supplement oxidation layer of the negative electrode lithium supplement ribbon on the negative electrode active material layer after the negative electrode lithium supplement sheet is formed to the area S0 of the negative electrode active material layer, the width of the coverage area, and a1/a0 in the length direction of the negative electrode sheet.
Note: the covering area is an area provided with a negative electrode lithium supplement belt in the negative electrode active material area of the negative electrode lithium supplement pole piece, and the non-covering area is an area which is not provided with the negative electrode lithium supplement belt in the negative electrode active material area of the negative electrode lithium supplement pole piece.
TABLE 3
Winding the graphite negative electrode lithium supplement pole piece, the lithium iron phosphate positive pole piece and the non-woven fabric diaphragm provided in application examples 1-10 to obtain a battery core, injecting carbonate electrolyte to obtain a lithium ion battery, and performing an electrochemical performance test under the following test conditions: the results of the normal temperature cycle 1C charge, 1C discharge, and a charge window of 2.5 to 3.65V are shown in Table 4.
TABLE 4
From the data results of the application example 2 and the application examples 4 and 5, it can be known that the angle formed by the starting point-end point connecting line in the width direction in the negative electrode lithium supplement strip and the length direction of the negative electrode lithium supplement pole piece is too small, and when the angle is smaller than 30 degrees or larger than 150 degrees, powder falling and peeling force reduction can occur, so that the first effect and the cycle life are reduced.
From the data results of application example 2 and application examples 8 and 9, it is understood that too small S1/S0 is not favorable for uniform lithium supplement, resulting in increase of dead lithium residue, and too large is hindered in heat diffusion.
As can be seen from the data results of application examples 1 and 10, with the smooth-surfaced, non-zoned lithium tape of comparative example 3, it was difficult to achieve rapid heat transfer, resulting in a decrease in the first efficiency and cycle of the battery.
In conclusion, the area is arranged in the negative electrode lithium supplement lithium strip, the criss-cross heat diffusion and electrolyte infiltration network is formed in the area, the gas production problem caused by poor or slow electrode piece infiltration after the negative electrode pole piece is covered by the lithium strip is solved, the dissolving efficiency of the metal lithium in the negative electrode is improved, and the lithium supplement effect of the negative electrode is effectively improved. Meanwhile, the thickness of the lithium belt can be increased under the same lithium supplement amount, the lithium belt-pole piece combination efficiency is improved, and the lithium supplement precision of the battery is also improved. When the negative electrode lithium-supplement lithium strip provided by the invention is applied to a negative electrode plate to obtain a battery, the first effect under 1C can reach more than 95%, and the capacity retention rate after circulation for 2000 times can reach more than 96%.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The negative electrode lithium supplement lithium strip is characterized in that the thickness of the negative electrode lithium supplement lithium strip is 3-10 mu m, and at least one region is arranged on the surface of the negative electrode lithium supplement lithium strip.
2. The negative lithium-supplemented lithium strip according to claim 1, wherein the shape of the region comprises any one of a rectangle, a square, a circle, an ellipse, a fingerprint, an island or a fish scale or a combination of at least two of the shapes;
preferably, the regions are distributed on the surface of the negative electrode lithium supplement lithium belt in a continuous state or a discontinuous state;
preferably, the maximum length of the area is 100-500 mm, and the maximum width is 50-3000 μm;
preferably, when the regions are distributed in a discontinuous state, the interval between each region is 10-1000 μm independently.
3. The negative lithium-supplemented lithium tape of claim 1 or 2, wherein the negative lithium-supplemented lithium tape is doped with a non-lithium element comprising any one or a combination of at least two of Al, Sn, Si, or Mg;
preferably, the mass of the non-lithium element is 0.01-2% of the mass of the negative electrode lithium-supplementing lithium tape.
4. A method of preparing a negative lithium-supplemented lithium strip according to any one of claims 1 to 3, characterized in that it comprises the following steps:
(1) mixing molten metal lithium and non-lithium elements, and pressing to obtain an initial lithium belt;
(2) and (2) carrying out calendering treatment on the initial lithium strip obtained in the step (1) to enable the rolling linear speed ratio of the fast and slow rollers to be 1-50%, so as to obtain the negative electrode lithium supplement lithium strip.
5. The method for preparing a lithium-supplemented negative electrode lithium strip according to claim 4, wherein the thickness of the initial lithium strip in step (1) is 30 μm to 30mm, preferably 50 μm to 5 mm;
preferably, the width of the initial lithium strip in the step (1) is 10-1000 mm;
preferably, the pressure of the calendering treatment in the step (2) is 1-5T, and preferably 1-3T.
6. The method for preparing the lithium-supplemented negative electrode strip according to claim 4 or 5, wherein in the rolling treatment in the step (2), the roller spacing is 40-110 μm, preferably 50-80 μm;
preferably, the rolling linear speed ratio of the fast and slow rollers in the step (2) is 2-30%;
preferably, in the rolling treatment in the step (2), the rolling speed is 5-100 m/min, preferably 20-100 m/min.
7. The method for preparing the lithium-supplemented negative electrode strip according to any one of claims 4 to 6, wherein the method comprises the following steps:
(1) mixing molten metal lithium and non-lithium elements, and pressing to obtain an initial lithium belt with the width of 10-400 mm and the thickness of 1-5 mm;
(2) and (2) conveying the initial lithium strip obtained in the step (1), and then performing calendering treatment at a calendering speed of 20-100 m/min by adopting a pressure of 1-3T, wherein the distance between rollers is kept to be 50-80 mu m, and the ratio of the rolling linear speeds of the fast roller and the slow roller is 2-30%, so as to obtain the negative electrode lithium supplement strip.
8. A negative electrode lithium supplementing pole piece, which is characterized in that the negative electrode lithium supplementing pole piece comprises a negative electrode current collector, a negative electrode active material layer arranged on at least one surface of the negative electrode current collector, and at least one negative electrode lithium supplementing lithium strip which is arranged on the surface of the negative electrode active material layer away from the current collector and is according to any one of claims 1 to 3.
9. The negative electrode lithium supplement electrode sheet according to claim 8, wherein the mass of the negative electrode lithium supplement lithium ribbon is 0.1 to 2%, preferably 0.5 to 1.5%, of the mass of the negative electrode active material layer;
preferably, the angle formed by the tangential direction of any point in the negative electrode lithium supplementing strip and the length direction of the negative electrode lithium supplementing pole piece is 30-150 degrees;
preferably, the negative electrode lithium supplementing lithium strip covers the surface of the negative electrode active material coating to form a covering area, a gap between the negative electrode lithium supplementing lithium strips forms a non-covering area, and the width ratio of the covering area to the non-covering area along the length direction of the pole piece is 0.1-0.99, preferably 0.2-0.8;
preferably, along the width direction of the negative electrode lithium supplement plate, the length of the part, covered by the negative electrode active material layer, of the negative electrode lithium supplement lithium strip is A1, and the length of the part, uncovered by the negative electrode active material layer, of the negative electrode lithium supplement lithium strip is A0, wherein A1/A0 is more than 16, and preferably A1/A0 is 20-200;
preferably, after the negative electrode lithium supplement electrode sheet is formed, the ratio S1/S0 of the sum S1 of the projection areas of the residual lithium supplement oxidation layer of the negative electrode lithium supplement lithium belt on the negative electrode active material layer to the area S0 of the negative electrode active material layer is 19.6-78.4%;
preferably, a part of lithium in the negative electrode lithium-supplementing strip on the surface of the negative electrode active material layer forms a second lithium intercalation compound under the action of an electrolyte, the second lithium intercalation compound exists on the surface of the negative electrode active material layer, and the second lithium intercalation compound is in a discontinuous state of interval distribution on the surface of the negative electrode active material layer;
preferably, the second lithium insertion compound is lithium oxide.
10. A lithium ion battery, characterized in that the lithium ion battery comprises the negative electrode lithium supplement pole piece according to claim 8 or 9.
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