CN114156496A - High-power primary lithium-manganese soft package battery and manufacturing method thereof - Google Patents
High-power primary lithium-manganese soft package battery and manufacturing method thereof Download PDFInfo
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 title claims abstract description 23
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 140
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 34
- 238000000576 coating method Methods 0.000 claims abstract description 21
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010949 copper Substances 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims description 20
- 238000007789 sealing Methods 0.000 claims description 18
- 238000003466 welding Methods 0.000 claims description 18
- 239000002033 PVDF binder Substances 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 10
- 239000006230 acetylene black Substances 0.000 claims description 8
- 238000007580 dry-mixing Methods 0.000 claims description 8
- 238000010030 laminating Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 238000004898 kneading Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000002347 injection Methods 0.000 claims description 6
- 239000007924 injection Substances 0.000 claims description 6
- 239000002985 plastic film Substances 0.000 claims description 6
- 229920006255 plastic film Polymers 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- 238000010276 construction Methods 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910000570 Cupronickel Inorganic materials 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 150000002641 lithium Chemical class 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 238000004804 winding Methods 0.000 abstract description 8
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 description 8
- 238000003475 lamination Methods 0.000 description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000011267 electrode slurry Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 210000005069 ears Anatomy 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
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- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/005—Devices for making primary cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the technical field of primary lithium batteries, and discloses a high-power primary lithium-manganese soft package battery and a manufacturing method thereof. The battery structure comprises an upper layer of diaphragm, a lower layer of diaphragm and a middle layer of lithium belt welded with a copper nickel-plated tab, wherein a manganese dioxide single-stage sheet with an aluminum tab is placed on the three-layer structure, and then the three-layer structure is folded in a Z shape or a winding shape, after one layer is folded, a manganese dioxide single-stage sheet is placed and then continuously folded, all the aluminum tabs after being folded are overlapped together to be welded with an outer tab, and a final naked battery core is formed. The invention relates to improvement of procedures such as material preparation, coating, naked cell manufacturing and the like, so as to realize high power performance of a lithium manganese battery.
Description
Technical Field
The invention belongs to the technical field of primary lithium batteries, and particularly relates to a high-power primary lithium-manganese soft package battery and a manufacturing method thereof.
Background
The lithium manganese battery electrode forming process mainly comprises a film pressing method and a paste coating method at present, and has the advantages of high resistance, high solid density, low production efficiency, poor rate capability, difficult control of surface density and poor electrode uniformity.
The traditional primary lithium-manganese soft package battery generally adopts a winding structure, is low in processing difficulty and easy for continuous production, but because the positive and negative electrodes of the battery are unipolar ears, the resistance of a pole piece film is large, the large-current discharge performance is poor, the lamination structure is adopted to be equivalent to the parallel connection of a plurality of small batteries, the internal resistance of the battery is effectively reduced, the high power performance of the battery can be effectively improved, but because the texture of a lithium belt is soft, the fold deformation is easily caused when die cutting molding and subsequent lamination are carried out, and the processing difficulty is large.
CN 102751476B patent discloses a composition and preparation method of lithium manganese positive electrode slurry suitable for coating process, sodium carboxymethylcellulose (CMC) and styrene butadiene rubber emulsion (SBR) are used as binder, and deionized water is used as solvent. And (3) baking electrolytic manganese dioxide, mixing the baked electrolytic manganese dioxide with conductive carbon black and colloidal graphite, mixing deionized water and sodium carboxymethylcellulose, stirring to form viscous liquid, adding dry powder into the viscous liquid in several times, then adding styrene-butadiene rubber emulsion, continuously stirring, and adjusting the rotating speed to finish the preparation of the slurry. The binder of sodium carboxymethylcellulose and styrene-butadiene rubber emulsion positive electrode slurry is adopted, so that the stirring time required by batching is long, the slurry dispersion difficulty is high, the processability of a pole piece is poor, and the problems of powder falling and the like are easy to occur.
The patent CN 112086655A discloses a low-temperature high-power lithium-manganese battery and a preparation method thereof, the process is as follows: preparing a graphene-based manganese dioxide positive plate, preparing a lithium-carbon composite negative electrode, preparing a microporous ceramic diaphragm, preparing a dry battery core and assembling a battery, wherein the positive plate and the negative plate are respectively the graphene-based manganese dioxide positive plate and the lithium-carbon composite negative plate, positive plate reserved lugs are arranged on the front surface and the back surface of the positive plate, and negative plate reserved lugs are arranged on the front surface and the back surface of the negative plate. The positive plate, the ceramic diaphragm, the negative plate and the ceramic diaphragm are sequentially and repeatedly laminated to form the dry cell. The lithium-carbon composite negative electrode reduces the energy density of the lithium negative electrode, and is immature in production process and high in production cost as a novel material at present.
Disclosure of Invention
In view of the defects in the prior art, the invention provides a high-power primary lithium manganese soft package battery and a manufacturing method thereof, which are used for effectively solving the technical problems in the background art and relate to the improvement of working procedures such as material preparation, coating, naked cell manufacturing and the like.
The above purpose of the invention is realized by the following technical scheme:
the utility model provides a lithium manganese laminate polymer battery once of high power, is by three layer construction according to the folding or the folding mode of Z type of coiling folding repeated folding 2 ~ 30 times, three layer construction includes diaphragm A, welding in proper order has lithium area, diaphragm B of copper nickel plating utmost point ear, and diaphragm A is equipped with the manganese dioxide single-level piece from taking aluminium utmost point ear.
A manufacturing method of a high-power primary lithium-manganese soft package battery comprises the following steps:
step S1, dry-mixing the transformed electrolytic manganese dioxide, the conductive agent and the binder powder, and then gradually adding the solvent for kneading and dispersing to obtain manganese dioxide slurry which is uniformly mixed;
step S2, uniformly coating the manganese dioxide slurry in the step S1 on two sides of a current collector aluminum foil pole piece by using a coating machine, baking the current collector aluminum foil pole piece by using an oven, rolling the pole piece by using a roller, and die-cutting the rolled pole piece into a manganese dioxide single pole piece and reserving an aluminum pole tab;
step S3, welding a tab on a lithium belt, paying attention to the position and the direction of the tab after welding, sequentially laminating a diaphragm A, the lithium belt welded with the tab and a diaphragm B, folding after laminating, inserting a manganese dioxide single-pole piece into the laminated lithium belt, enabling the insertion position to be opposite to the positive pole, repeatedly folding for a plurality of times, and fixing by using a stop glue; the aluminum tabs reserved on the manganese dioxide single pole piece are superposed in the same row and then welded with the outer tabs to form a naked battery core;
and S4, filling the bare cell in the step S3 into an aluminum plastic film for top side sealing, performing liquid injection and pre-sealing after vacuum baking, performing pre-discharge after standing at normal temperature, performing secondary sealing and exhausting after standing at high temperature, and finishing the cell manufacturing.
Further, in step S1, the binder is polyvinylidene fluoride PVDF, the conductive agent is acetylene black, and the solvent is N-methylpyrrolidone NMP; the PVDF binder accounts for 2-5% by mass, the acetylene black accounts for 5-10% by mass, and the balance is transformed electrolytic manganese dioxide.
Further, in the step S1, the stirring linear speed is 5-15m/S during the dry mixing, kneading and dispersing processes, and the time is 3-5h, so that the viscosity of the manganese dioxide slurry is 3000-.
Further, the manganese dioxide slurry in the step S2 has a coating area density of 50-100mg/cm2。
Furthermore, the loss ratio of the pole piece after baking in the oven in the step S2 is controlled below 0.3%.
Further, in the step S3, the tab is a copper nickel-plated tab, and the position of the copper nickel-plated tab is on the same side or opposite to the position of the aluminum tab of the manganese dioxide single-pole piece after welding.
Further, the folding mode in the step S3 includes roll-to-roll folding or Z-folding, the number of times of the repeated folding is 2-30 times, and the folding is performed according to the required width of 30-150mm after the lamination.
Further, in the vacuum baking process of the step S4, the vacuum is less than or equal to-90 Kpa, the baking temperature is 80-100 ℃, and the baking time is 4-24 h.
Further, the normal-temperature standing process of the step S4 is carried out at the temperature of 15-30 ℃ for 12-48 h; in the high-temperature standing process, the temperature is 40-60 ℃, and the time is 12-48 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) due to the lipophilic characteristics of manganese dioxide and a conductive agent, the composite material is more fully dissolved in an NMP solvent system and is easier to disperse, so that the preparation of slurry can be completed in a shorter time by using dry mixing and stirring of a PVDF/NMP system, and in addition, the possibility of pole piece moisture residue after water system slurry coating can be greatly reduced by using oil system stirring, and the failure of a battery cell is caused.
(2) The slurry using the PVDF/NMP system has good stability, the pole piece coating, the internal porosity of the coating and the conductive network are distributed more uniformly during coating, and the electronic and ionic impedance of the pole piece can be reduced; the pole piece using the PVDF/NMP system has better adhesion, can reduce the contact impedance between the coating and the current collector, and can properly reduce the use proportion of the adhesive due to the better adhesion, thereby improving the proportion of active substances and improving the energy density.
(3) The folding naked battery cell structure provided by the invention can take the winding type and lamination type advantages into consideration, can obviously reduce the processing difficulty compared with the lamination type structure, and can basically keep the power performance of the battery cell unchanged while improving the production efficiency; compared with a winding structure, the processing difficulty of the battery cell is basically kept unchanged while the power performance of the battery cell is improved.
Drawings
The invention is further illustrated with reference to the following figures and examples.
FIG. 1 is a diagram showing the pre-rolled folding effect of a manganese dioxide monolithic sheet;
FIG. 2 is a diagram illustrating the effect after being folded in a roll form;
FIG. 3 is a diagram showing the effect of a rolled manganese dioxide monolithic sheet before Z-folding or before winding without pre-placing the manganese dioxide monolithic sheet;
FIG. 4 is a Z-shaped folded effect illustration;
FIG. 5 is a 0.05C rate discharge comparison curve for a primary lithium manganese battery;
FIG. 6 is a 0.3C rate discharge comparison curve for a primary lithium manganese battery;
FIG. 7 shows that the aluminum tabs of the nickel-plated copper tab and the manganese dioxide single-pole piece are positioned on the same side after welding;
FIG. 8 shows the position of the copper nickel-plated tab directly facing the aluminum tab of the manganese dioxide single-pole piece after welding.
In the figure, 1, a diaphragm A, 2, a lithium belt, 3, a manganese dioxide single-stage sheet, 4, an aluminum tab, 5, a copper nickel-plated tab and 6, a diaphragm B.
Detailed Description
The invention is described in more detail below with reference to specific examples, without limiting the scope of the invention. Unless otherwise specified, the experimental methods adopted by the invention are all conventional methods, and experimental equipment, materials, reagents and the like used in the experimental method can be obtained from commercial sources.
Example 1
Step one, dry-mixing 89% of transformed electrolytic manganese dioxide, 6% of acetylene black and 5% of PVDF, gradually adding NMP for kneading, and dispersing at a high speed to control the viscosity of the slurry to 7000 +/-1000 mpas.
Step two, coating the obtained manganese dioxide slurry, wherein the coating surface density is 80mg/cm2The weight loss ratio of the coated pole piece is about 0.2 percent; then rolling the pole piece, die-cutting the rolled pole piece into a manganese dioxide single pole piece 3 and reserving an aluminum pole lug 4;
and step three, welding a copper nickel-plated tab 5 on the lithium belt 2, enabling the welded copper nickel-plated tab 5 and an aluminum tab 4 of the manganese dioxide single-pole piece 3 to be at the same side, and then sequentially laminating a diaphragm A1, the lithium belt 2 with the tabs welded and a diaphragm B6. Putting a manganese dioxide single-pole piece 3 on the laminated three-layer structure, folding the three-layer structure together, folding the three-layer structure for one layer, putting another manganese dioxide single-pole piece 3, and continuing folding the folded layer; the manganese dioxide single-pole piece 3 can also be placed at a predetermined position as shown in fig. 1; after all the manganese dioxide single pole pieces 3 are placed, the manganese dioxide single pole pieces are folded in a winding manner, as shown in figure 2. The manganese dioxide single-pole piece 3 is put into the position, the situation that the finally reserved aluminum pole lug is overlapped with the previous positive pole is guaranteed, and the aluminum pole lug is fixed by using stop glue after being repeated for 20 times; and (3) overlapping the aluminum tabs 4 reserved on the manganese dioxide single pole piece 3 in the same row, and then welding the outer tabs to prepare the naked battery core.
Step four, placing the bare cell into an aluminum-plastic film for top side sealing, carrying out vacuum baking under the conditions that the vacuum is less than or equal to-90 Kpa, the baking temperature is 80-100 ℃, the baking time is 4-24 hours, then carrying out liquid injection and pre-sealing, carrying out pre-discharging after standing at the normal temperature under the conditions that the temperature is 15-30 ℃ and the time is 12-48 hours, then carrying out high-temperature standing under the conditions that the temperature is 40-60 ℃ and the time is 12-48 hours, finally carrying out secondary sealing and exhausting, completing cell manufacturing, and selecting the cell to carry out constant current discharging to 2.0V by using currents of 0.05C and 0.3C respectively.
Example 2
Step one, dry-mixing 92% of transformed electrolytic manganese dioxide, 5% of acetylene black and 3% of PVDF, gradually adding NMP for kneading, and dispersing at a high speed to control the viscosity of the slurry to be 5000 +/-1000 mpas.
Step two, coating the obtained manganese dioxide slurry, wherein the coating surface density is 70mg/cm2The weight loss ratio of the coated pole piece is about 0.2 percent; then rolling the pole piece, die-cutting the rolled pole piece into a manganese dioxide single pole piece 3 and reserving an aluminum pole lug 4;
and step three, welding a copper nickel-plated tab 5 on the lithium belt 2, enabling the welded copper nickel-plated tab 5 and an aluminum tab 4 of the manganese dioxide single-pole piece 3 to be in opposite positions, and then sequentially laminating a diaphragm A1, the lithium belt 2 with the tabs welded and a diaphragm B6. Putting a manganese dioxide single-pole piece 3 on the laminated three-layer structure, folding the three-layer structure together, folding the three-layer structure for one layer, putting another manganese dioxide single-pole piece 3, and continuing folding the folded layer; the manganese dioxide single-pole piece 3 can also be placed at a predetermined position as shown in fig. 1; after all the manganese dioxide single pole pieces 3 are placed, the manganese dioxide single pole pieces are folded in a winding manner, as shown in figure 2. The manganese dioxide single-pole piece 3 is put into the position, the situation that the finally reserved aluminum pole lug is overlapped with the previous positive pole is guaranteed, and the aluminum pole lug is fixed by using stop glue after repeating for 10 times; and (3) overlapping the aluminum tabs 4 reserved on the manganese dioxide single pole piece 3 in the same row, and then welding the outer tabs to prepare the naked battery core.
Step four, placing the bare cell into an aluminum-plastic film for top side sealing, carrying out vacuum baking under the conditions that the vacuum is less than or equal to-90 Kpa, the baking temperature is 80-100 ℃, the baking time is 4-24 hours, then carrying out liquid injection and pre-sealing, carrying out pre-discharging after standing at the normal temperature under the conditions that the temperature is 15-30 ℃ and the time is 12-48 hours, then carrying out high-temperature standing under the conditions that the temperature is 40-60 ℃ and the time is 12-48 hours, finally carrying out secondary sealing and exhausting, completing cell manufacturing, and selecting the cell to carry out constant current discharging to 2.0V by using currents of 0.05C and 0.3C respectively.
Example 3
Step one, dry-mixing 93% of transformed electrolytic manganese dioxide, 5% of acetylene black and 2% of PVDF, gradually adding NMP for kneading, and dispersing at a high speed to control the viscosity of the slurry to be 5000 +/-1000 mpas.
Step two, the obtainedManganese dioxide slurry is coated, and the coating surface density is 60mg/cm2The weight loss ratio of the coated pole piece is about 0.2 percent; then rolling the pole piece, die-cutting the rolled pole piece into a manganese dioxide single pole piece 3 and reserving an aluminum pole lug 4;
and step three, welding a copper nickel-plated tab 5 on the lithium belt 2, enabling the welded copper nickel-plated tab 5 and an aluminum tab 4 of the manganese dioxide single-pole piece 3 to be in opposite positions, and then sequentially laminating a diaphragm A1, the lithium belt 2 with the tabs welded and a diaphragm B6. Placing a manganese dioxide single-pole piece 3 on the laminated three-layer structure, and performing Z-shaped folding on the three-layer structure to wrap the manganese dioxide single-pole piece 3 as shown in figure 3; then, continuously putting a manganese dioxide single-pole piece 3 and then folding the manganese dioxide single-pole piece in a reciprocating manner, as shown in fig. 4, the putting position of the manganese dioxide single-pole piece 3 needs to be ensured to be at the same position as the previous positive pole, so that the finally reserved aluminum pole ear can be ensured to be overlapped, and the aluminum pole ear is fixed by using stop glue after repeating for 10 times; and (3) overlapping the aluminum tabs 4 reserved on the manganese dioxide single pole piece 3 in the same row, and then welding the outer tabs to prepare the naked battery core.
Step four, placing the bare cell into an aluminum-plastic film for top side sealing, carrying out vacuum baking under the conditions that the vacuum is less than or equal to-90 Kpa, the baking temperature is 80-100 ℃, the baking time is 4-24 hours, then carrying out liquid injection and pre-sealing, carrying out pre-discharging after standing at the normal temperature under the conditions that the temperature is 15-30 ℃ and the time is 12-48 hours, then carrying out high-temperature standing under the conditions that the temperature is 40-60 ℃ and the time is 12-48 hours, finally carrying out secondary sealing and exhausting, completing cell manufacturing, and selecting the cell to carry out constant current discharging to 2.0V by using currents of 0.05C and 0.3C respectively.
Comparative example
Step one, preparing the transformed electrolytic manganese dioxide 88%, acetylene black 6% and CMC 2% SBR 4% into slurry with the viscosity of 5000 +/-1000 mpas.
Step two, coating the obtained manganese dioxide slurry, wherein the coating surface density is 70mg/cm2The weight loss ratio of the coated pole piece is about 0.2 percent; rolling the pole piece, and welding an outer pole lug on the rolled manganese dioxide pole piece;
step three, welding a copper nickel-plated tab on a lithium belt, then sequentially laminating a diaphragm, the lithium belt welded with the tab, the diaphragm and a manganese dioxide pole piece welded with an outer tab, and winding according to the required size after lamination to finish fixing by using a stop rubber to prepare a bare cell;
step four, placing the bare cell into an aluminum-plastic film for top side sealing, carrying out vacuum baking under the conditions that the vacuum is less than or equal to-90 Kpa, the baking temperature is 80-100 ℃, the baking time is 4-24 hours, then carrying out liquid injection and pre-sealing, carrying out pre-discharging after standing at the normal temperature under the conditions that the temperature is 15-30 ℃ and the time is 12-48 hours, then carrying out high-temperature standing under the conditions that the temperature is 40-60 ℃ and the time is 12-48 hours, finally carrying out secondary sealing and exhausting, completing cell manufacturing, and selecting the cell to carry out constant current discharging to 2.0V by using currents of 0.05C and 0.3C respectively.
The embodiments described above are merely preferred embodiments of the invention, rather than all possible embodiments of the invention. Any obvious modifications to the above would be obvious to those of ordinary skill in the art, but would not bring the invention so modified beyond the spirit and scope of the present invention.
Claims (10)
1. The utility model provides a lithium manganese laminate polymer battery is once carried to high power, characterized by is by three layer construction fold according to the coiling formula or the folding mode of Z type is repeated folding 2 ~ 30 times, three layer construction includes diaphragm A (1), welding in proper order has lithium area (2), diaphragm B (6) of copper nickel plating utmost point ear (5), and diaphragm A (1) is equipped with manganese dioxide single-level piece (3) from taking aluminium utmost point ear (4).
2. A manufacturing method of a high-power primary lithium-manganese soft package battery is characterized by comprising the following steps:
step S1, dry-mixing the transformed electrolytic manganese dioxide, the conductive agent and the binder powder, and then gradually adding the solvent for kneading and dispersing to obtain manganese dioxide slurry which is uniformly mixed;
step S2, uniformly coating the manganese dioxide slurry in the step S1 on two sides of a current collector aluminum foil pole piece by using a coating machine, baking the current collector aluminum foil pole piece by using an oven, rolling the pole piece by using a roller, die-cutting the rolled pole piece into a manganese dioxide single pole piece (3) and reserving an aluminum tab (4);
step S3, welding a tab on a lithium belt, paying attention to the position and the direction of the tab after welding, sequentially laminating a diaphragm A (1), the lithium belt (2) with the tab welded and a diaphragm B (6), folding after laminating, inserting a manganese dioxide single-pole piece (3) into the laminated lithium belt, enabling the inserted position to be opposite to the positive pole, repeatedly folding for a plurality of times, and fixing by using a stop glue; aluminum tabs (4) reserved on the manganese dioxide single-pole piece (3) are superposed in the same row and then welded with outer tabs to form a bare cell;
and S4, filling the bare cell in the step S3 into an aluminum plastic film for top side sealing, performing liquid injection and pre-sealing after vacuum baking, performing pre-discharge after standing at normal temperature, performing secondary sealing and exhausting after standing at high temperature, and finishing the cell manufacturing.
3. The manufacturing method of the high-power primary lithium manganese soft package battery according to claim 2, wherein in step S1, the binder is polyvinylidene fluoride (PVDF), the conductive agent is acetylene black, and the solvent is N-methylpyrrolidone (NMP); the PVDF binder accounts for 2-5% by mass, the acetylene black accounts for 5-10% by mass, and the balance is transformed electrolytic manganese dioxide.
4. The method as claimed in claim 2, wherein the stirring linear speed during the dry mixing, kneading and dispersing process in step S1 is 5-15m/S for 3-5h, and the viscosity of the manganese dioxide slurry obtained is 3000-.
5. The method for manufacturing a high-power primary lithium manganese pouch battery according to claim 2, wherein the manganese dioxide slurry has a coating areal density of 50-100mg/cm2 in step S2.
6. The manufacturing method of the high-power primary lithium manganese soft package battery as claimed in claim 2, wherein the loss-to-weight ratio of the pole piece after baking in the oven in step S2 is controlled below 0.3%.
7. The manufacturing method of the high-power primary lithium manganese soft package battery according to claim 2, characterized in that in step S3, the tab is a copper nickel-plated tab (5), and the positions of the copper nickel-plated tab (5) and the aluminum tab (4) of the manganese dioxide single-pole piece (3) are on the same side or opposite to each other after welding.
8. The manufacturing method of the high-power primary lithium manganese soft package battery according to claim 2, wherein the folding mode in the step S3 includes roll folding or Z-folding, the number of times of the folding is 2-30, and the folding is performed according to the required width of 30-150mm after the stacking.
9. The method for manufacturing the high-power primary lithium-manganese soft package battery as claimed in claim 2, wherein in the step S4, the vacuum baking process is performed at a vacuum of less than or equal to-90 Kpa, the baking temperature is 80-100 ℃, and the baking time is 4-24 h.
10. The manufacturing method of the high-power primary lithium manganese soft package battery according to claim 2, wherein the normal-temperature shelf process of step S4 is carried out at 15-30 ℃ for 12-48 h; in the high-temperature standing process, the temperature is 40-60 ℃, and the time is 12-48 h.
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| CN102013528A (en) * | 2009-09-08 | 2011-04-13 | 赵宽 | Improved lithium ion battery manufacture process |
| CN102456907A (en) * | 2010-10-21 | 2012-05-16 | 力佳电源科技(深圳)有限公司 | Electrical core structure of square cell and preparation method thereof |
| JP2018120811A (en) * | 2017-01-27 | 2018-08-02 | マクセルホールディングス株式会社 | Lithium ion secondary battery and method for manufacturing the same |
| CN112086655A (en) * | 2020-10-15 | 2020-12-15 | 隆能科技(南通)有限公司 | Low-temperature high-power lithium-manganese battery and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102013528A (en) * | 2009-09-08 | 2011-04-13 | 赵宽 | Improved lithium ion battery manufacture process |
| CN102456907A (en) * | 2010-10-21 | 2012-05-16 | 力佳电源科技(深圳)有限公司 | Electrical core structure of square cell and preparation method thereof |
| JP2018120811A (en) * | 2017-01-27 | 2018-08-02 | マクセルホールディングス株式会社 | Lithium ion secondary battery and method for manufacturing the same |
| CN112086655A (en) * | 2020-10-15 | 2020-12-15 | 隆能科技(南通)有限公司 | Low-temperature high-power lithium-manganese battery and preparation method thereof |
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