CN115036462A - Pure dry method sodium ion battery cathode, preparation method and battery thereof - Google Patents
Pure dry method sodium ion battery cathode, preparation method and battery thereof Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 44
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 42
- 239000003292 glue Substances 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000013543 active substance Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 229910021385 hard carbon Inorganic materials 0.000 claims description 38
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 38
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 35
- 239000006245 Carbon black Super-P Substances 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 30
- 238000005303 weighing Methods 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 16
- 238000005520 cutting process Methods 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 238000013329 compounding Methods 0.000 claims description 11
- 239000011888 foil Substances 0.000 claims description 11
- 239000006258 conductive agent Substances 0.000 claims description 9
- 206010061592 cardiac fibrillation Diseases 0.000 claims description 7
- 230000002600 fibrillogenic effect Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- -1 LTO Substances 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 238000005096 rolling process Methods 0.000 claims description 5
- 229910021383 artificial graphite Inorganic materials 0.000 claims description 4
- 229910021384 soft carbon Inorganic materials 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 238000003490 calendering Methods 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 239000004020 conductor Substances 0.000 claims description 3
- 238000007580 dry-mixing Methods 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000005864 Sulphur Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010073 coating (rubber) Methods 0.000 claims 4
- 230000001629 suppression Effects 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 34
- 239000011247 coating layer Substances 0.000 abstract description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 16
- 229910052708 sodium Inorganic materials 0.000 description 16
- 239000011734 sodium Substances 0.000 description 16
- 239000011148 porous material Substances 0.000 description 14
- 238000003860 storage Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 159000000000 sodium salts Chemical group 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- QMGYPNKICQJHLN-UHFFFAOYSA-M Carboxymethylcellulose cellulose carboxymethyl ether Chemical compound [Na+].CC([O-])=O.OCC(O)C(O)C(O)C(O)C=O QMGYPNKICQJHLN-UHFFFAOYSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 239000000839 emulsion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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 discloses a pure dry method sodium ion battery cathode, a preparation method and a battery thereof, and the pure dry method sodium ion battery cathode comprises a current collector layer, conductive glue coating layers and fibrillating elastic layers, wherein the two side surfaces of the current collector layer respectively comprise the conductive glue coating layers, the outer sides of the two conductive glue coating layers are respectively provided with the fibrillating elastic layers, the current collector layer, the conductive glue coating layers and the fibrillating elastic layers are thermally compounded into a sheet-shaped cathode sheet, the fibrillating elastic layers comprise a plurality of elastic reticular structures, each fibrillating elastic layer comprises a mixture consisting of active substance particles, conductive particles and fibrillatable resin, the fibrillatable resin is in an interlaced fibril shape and forms the elastic reticular structure, and the elastic reticular structures inhibit the expansion of the cathode sheet, so that the battery keeps higher consistency and stability.
Description
Technical Field
The invention belongs to the field of sodium batteries, and particularly relates to a pure dry method sodium ion battery cathode, a preparation method and a battery thereof.
Background
Compared with a lithium ion battery, the sodium ion battery has lower energy density and the safety performance which is equal to that of lithium iron phosphate and is superior to a ternary battery; the main advantage of this is low cost. In recent years, with the shortage of lithium resources, the price has rapidly increased, and attention has been paid to a sodium ion battery with lower cost and wide resource distribution. Meanwhile, the development of an energy storage market with lower requirements on energy density finds a new application scene in the industrialization of the sodium-ion battery, and the research on the sodium-ion battery is facing to the blowout-type growth, which marks the arrival of the industrialization era of the sodium-ion battery.
The positive electrode material of the sodium-ion battery has a route of layered metal oxide, polyanion compound and Prussian blue analogue; the negative electrode material mainly comprises soft carbon, hard carbon and soft-hard composite amorphous carbon; the electrolyte is sodium salt, and the solvent can be conventional solvents such as EC, EMC, DMC, PC and the like; the separator is PP or PE. In addition, since sodium and aluminum do not undergo an alloying reaction, an inexpensive aluminum foil can be used as the negative electrode current collector of the sodium ion battery. But in contrast to lithium ions
Radius of sodium ion
Larger, the diffusion kinetics are more retarded.
The principle of negative electrode sodium storage is that sodium ions are reversibly stored and released through the alloy reaction of the sodium ions and negative electrode materials or the pore adsorption type sodium storage among negative electrode particles. After the sodium ion battery is charged, the volume expansion of the negative electrode is large due to the alloy reaction; the adsorption type sodium storage is to store active sodium through the pores among the cathode particles, the sodium storage capacity of the hard carbon is 280-500mAh/g according to the pore structure and micropore distribution condition, and the better cathode pore structure can greatly improve the sodium storage capacity of the hard carbon adsorption type sodium storage. Therefore, the method has high requirements on the micro-pore structure of the cathode, and the initial porosity, the rule degree, the porosity and the rule degree after the cathode is cycled, namely the consistency, can greatly influence the sodium storage capacity and the cycling stability of the cathode.
Disclosure of Invention
The purpose of the invention is as follows: in order to overcome the defects in the prior art, the invention provides a pure dry method sodium ion battery cathode, a preparation method and a battery thereof, which can inhibit the expansion of a battery cathode plate and keep the battery at higher consistency and stability.
The technical scheme is as follows: in order to achieve the purpose, the technical scheme of the invention is as follows:
the pure dry method sodium ion battery cathode comprises a current collecting layer, conductive glue coating layers and a fibrillating elastic layer, wherein the two side surfaces of the current collecting layer respectively comprise the conductive glue coating layers, the outer sides of the two conductive glue coating layers are respectively provided with the fibrillating elastic layer, the current collecting layer, the conductive glue coating layers and the fibrillating elastic layer are thermally compounded into a sheet-shaped cathode sheet, the fibrillating elastic layer internally comprises a plurality of elastic net-shaped structures, and the elastic net-shaped structures inhibit the expansion of the cathode sheet.
Further, the fibrillated elastic layer includes a mixture of active substance particles, conductive particles, and a fiberizable resin in the form of interwoven filaments that form an elastic network.
A method for preparing a pure dry method sodium ion battery cathode comprises the steps of dry mixing active substance particles, conductive particles and fiberizable resin according to the mass ratio, then performing fibrillation, and then extruding to prepare a self-supporting base electrode; carrying out multistage calendering and rolling on the base electrode, and then thermally compounding the base electrode with the glued current collector layer to obtain a finished negative plate;
wherein, the mass percentage of the fiberizable resin is 1-5%; the mass percentage of the conductive material is 1-5%; the mass percentage of the active substance particles is 90-98%.
Further, the active material particles include any one or more of hard carbon powder, soft carbon, sulfur, LTO, metal or alloy.
Further, the conductive particles are any one or more of carbon black super-p, KS-6, conductive graphite, carbon nanotubes, graphene and carbon fibers VGCF.
Further, the fiberizable resin is PTFE or modified PTFE.
Further, the active substance particles are hard carbon powder, the conductive particles are carbon black super-p, and the fiberizable resin is modified PTFE; and hard carbon powder: carbon black super-p: the mixing ratio of PTFE in parts by mass is 94:3:3 or 93:3: 4.
further, hard carbon powder: carbon black super-p: the mixing ratio of PTFE in parts by mass is 94:3:3 comprises the following preparation steps:
s1: weighing 94 parts by mass of hard carbon powder, wherein D50 is 4um, and adding into a planetary mixer;
s2: weighing 3 parts by mass of carbon black super-p, adding the carbon black super-p into hard carbon powder, and rotating and stirring for 30min to obtain powder A;
s3: weighing 3 parts by mass of modified PTFE powder with D50 of 0.5-2um, adding into the powder A, and rotationally stirring for 30min to obtain powder B;
s4: fibrillating powder B: fibrillating PTFE with a supersonic gas jet using a jet mill by drawing PTFE at a D50 range of 0.5-2um into filaments having a diameter of 10-100nm and a single length of 5-100um, interlacing the plurality of filaments into an elastic network, and uniformly embedding a hard carbon and carbon black super-p conductive agent in the network;
the mixed powder B after the fibrillation is put into an open mill, and a continuous basic negative plate is extruded from a double roller, the thickness is 100- 2 ；
S5: the basic negative plate smelted in the step S4 passes through a multi-stage calender, and the density of the extended part of the plate is controlled to be 7.0mg/cm 2 The thickness is 70 +/-2 um;
s6: placing two rolls of basic negative plates on the upper and lower surfaces of the glue-coated aluminum foil of the current collector layer respectively, and performing thermal compounding;
s7: and cutting and die-cutting the thermally compounded pole piece to obtain the cathode piece with the preset width and length.
Further, the hard carbon powder: carbon black super-p: the mixing ratio of PTFE in parts by mass is 93:3:4 comprises the following preparation steps:
s1: weighing 93 parts by mass of hard carbon powder, wherein D50 is 4um, and adding into a planetary stirrer;
s2: weighing 3 parts by mass of carbon black super-p, adding the carbon black super-p into artificial graphite powder, and rotating and stirring for 30min to obtain powder A;
s3: weighing 4 parts by mass of modified PTFE powder, wherein D50 is 0.5-2um, adding into the powder A, and rotating and stirring for 30min to obtain powder B;
s4: fibrillating the powder B: fibrillating PTFE with a supersonic gas jet using a jet mill by drawing PTFE at a D50 range of 0.5-2um into filaments having a diameter of 10-100nm and a single length of 5-100um, interlacing the plurality of filaments into an elastic network, and uniformly embedding a hard carbon and carbon black super-p conductive agent in the network;
the mixed powder B after the fibrillation is put into an open mill, and a continuous basic negative plate is extruded from a double roller, the thickness is 100- 2 ；
S5: the basic negative plate smelted in the step S4 passes through a multi-stage calender, and the density of the extended part of the plate is controlled to be 7.0mg/cm 2 The thickness is 70 +/-2 um;
s6: respectively placing 2 rolls of basic negative plates on the upper surface and the lower surface of the glue-coated aluminum foil of the current collector layer, and carrying out thermal compounding;
s7: and (3) cutting and die-cutting the thermally compounded pole piece to obtain the negative pole piece with the preset width and length.
A pure dry sodium ion battery comprises a battery core of a pure dry sodium ion battery cathode.
Has the advantages that: according to the negative plate of the ion battery, the negative electrode expansion can be effectively controlled, the sodium storage amount of the negative electrode is increased, the filaments are staggered to form a net structure, the negative active material and the conductive agent particles are placed in the net structure, so that the negative plate has a uniform and regular pore structure, the microscopic pores of the negative electrode have better consistency and stability in the charging and discharging processes, and the battery cycle is improved.
Drawings
FIG. 1 is a schematic sectional view of a negative electrode plate of a battery according to the present invention;
FIG. 2 is a microscopic representation of a fibrillated elastic layer of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings.
As shown in fig. 1 and fig. 2, the pure dry sodium ion battery negative electrode comprises a current collecting layer 1, conductive glue coating layers 2 and a fibrillating elastic layer 3, wherein the two side surfaces of the current collecting layer 1 respectively comprise the conductive glue coating layers 2, the outer sides of the two conductive glue coating layers 2 are respectively provided with the fibrillating elastic layer 3, the current collecting layer 1, the conductive glue coating layers 2 and the fibrillating elastic layer 3 are thermally compounded into a sheet-shaped negative electrode sheet, the fibrillating elastic layer 3 comprises a plurality of elastic net-shaped structures, and the elastic net-shaped structures inhibit the expansion of the negative electrode sheet.
As shown in fig. 2, the fibrillatable elastic layer 3 includes a mixture of active material particles 11, conductive particles 12 and fibrillatable resin 13, the fibrillatable resin is in an interlaced fibril shape and forms an elastic network structure, sodium storage gaps 14 for storing sodium ions are formed among the active material particles 11, the conductive particles 12 and the fibrillatable resin 13, when the sodium ions are stored in the sodium storage gaps among the particles, the expansion of the negative electrode can be effectively controlled through the elastic network structure, the sodium storage amount of the negative electrode is increased, the filaments are interlaced to form the network structure, the negative electrode active material and the conductive agent particles are placed in the network structure, so that the uniform and regular pore structure is provided, the microscopic pores of the negative electrode have better consistency and stability in the charging and discharging process, and the battery cycle is improved.
The negative electrode formula is compounded into a negative plate by using a fibrillating elastic layer containing a fibrillating binder and a gummed current collector; the fibrillating adhesive is sprayed with supersonic gas in a jet mill to form filaments with the diameter of 10nm-100um and the length of 5-100um, the filaments are staggered to form an elastic net structure, and the negative active material and the conductive agent particles are placed in the net structure. The former has a relatively more uniform and regular pore structure compared to the non-fibrillated adhesives. When the negative electrode is charged and expanded, the fibrils form an elastic net structure which can well inhibit the expansion of the negative electrode sheet; and simultaneously, the expansion of the negative electrode is more uniform in a microscopic mode, namely, the pores of the negative electrode after expansion or circulation are still more uniform and regular, and more sodium ions can be stably and reversibly adsorbed among the pores of the negative electrode.
A method for preparing a pure dry method sodium ion battery cathode comprises the steps of dry mixing active substance particles, conductive particles and fiberizable resin according to the mass part ratio, then fibrillating, and then extruding to prepare a self-supporting basic electrode; carrying out multistage calendering and rolling on the base electrode, and then thermally compounding the base electrode with the glued current collector layer to obtain a finished negative plate;
wherein, the mass percentage content of the fiberizable resin is 0.1-20%; preferably 1-5%; the mass percentage of the conductive material is 0.1-20%, preferably 1-5%; the mass percentage of the active substance particles is 60-99.8%, preferably 90-98%.
The active material particles comprise any one or more of hard carbon powder, soft carbon, sulphur, LTO, metal or alloy.
The conductive particles are any one or more of carbon black super-p, KS-6, conductive graphite, carbon nanotubes, graphene and carbon fibers VGCF.
The fiberizable resin is PTFE or modified PTFE, i.e., polytetrafluoroethylene.
Preferably, the active substance particles are hard carbon powder, the conductive particles are carbon black super-p, and the fiberizable resin is modified PTFE; and hard carbon powder: carbon black super-p: the mixing ratio of PTFE in parts by mass is 94:3:3 or 93:3: 4.
the first embodiment is as follows: hard carbon particles: carbon black super-p: the mass portion ratio of PTFE is 94:3: 3.
Cylindrical battery 18650, capacity 1000mAh, its preparation includes the following steps:
s1: weighing 20kg of hard carbon powder with D50 of 4um, and adding into a 30L planetary mixer;
s2: weighing 0.638kg of carbon black super-p, adding into the artificial graphite powder, revolving at 20rpm, rotating at 500rpm, and stirring for 30min to obtain powder A;
s3: weighing 0.638kg of modified PTFE powder with D50 of 0.5-2um, adding into the powder A, revolving at 20rpm, rotating at 500rpm, and stirring for 30 min; obtaining powder B;
s4: fibrillating powder B: using supersonic gas jet for jet mill to fibrillate PTFE, wherein D50 of PTFE of 0.5-2um is stretched into filaments of 10-100nm diameter and 5-100um length, and a plurality of filaments are interwoven into an elastic network, so that hard carbon particles and carbon black conductive agent are uniformly embedded in a net structure;
putting the mixed powder B after the fibrillation into an open mill, and extruding a continuous basic negative plate from a roll gap of 100-150 mu m at the speed of 20-30m/min, wherein the thickness of the negative plate is 100-110 mu m, and the surface density of the negative plate is 7.1mg/cm 2 ；
S5: the self-supporting basic negative plate milled in the step S4 is passed through a multi-stage calender under the pressure of 10-20t, and the density of the extended part of the plate is controlled to be 7.0mg/cm 2 The thickness is 70 +/-2 um;
s6: placing two rolls of self-supporting negative plates on the upper surface and the lower surface of a glue-coated aluminum foil of the current collector layer 1 respectively, and performing thermal compounding, wherein the thickness of a glue-coated aluminum foil substrate is 6 microns, and the thickness of each conductive glue-coated layer is 2 microns; compounding parameters: the temperature is 160 +/-2 ℃, the pressure is 10t, and the time is 5 s; the thickness of the compounded pole piece is 148 +/-2 um;
s7: and cutting and die cutting the hot compounded pole piece to obtain the negative pole piece with the length and the width of 450 mm and 59 mm.
The second embodiment: hard carbon particles: carbon black super-p: the mass part ratio of PTFE is 93:3: 4.
Cylindrical battery 18650, capacity 1000mAh, its preparation includes the following steps:
s1: weighing 19.78kg of hard carbon powder with D50 of 4um, and adding into a 30L planetary mixer;
s2: weighing 0.638kg of carbon black super-p, adding into the artificial graphite powder, revolving at 20rpm, rotating at 500rpm, and stirring for 30min to obtain powder A;
s3: weighing 0.85kg of modified PTFE powder with D50 of 0.5-2um, adding into the powder A, revolving at 20rpm, rotating at 500rpm, and stirring for 30 min; obtaining powder B;
s4: fibrillating the powder B: the PTFE is fibrillated by using supersonic gas jet with a jet mill, the fibrillating process is to stretch PTFE with D50 of 0.5-2um into filaments with the diameter of 10-100nm and the length of 5-100um, and a plurality of filaments are interwoven into an elastic network, and the hard carbon particles and the carbon black conductive agent are uniformly embedded into a net structure;
the mixed powder B after the fibrillation is put into an open mill, and a continuous basic negative plate is extruded out from a roll gap of 100 plus materials and 150 mu m at the speed of 20-30m/min, wherein the thickness is 100 plus materials and 110 mu m, and the areal density is 7.1mg/cm 2 ；
S5: the self-supporting basic negative plate milled in the step S4 is passed through a multi-stage calender under the pressure of 10-20t, and the density of the extended part of the plate is controlled to be 7.0mg/cm 2 The thickness is 70 +/-2 um;
s6: placing two rolls of self-supporting negative plates on the upper surface and the lower surface of a glue-coated aluminum foil of the current collector layer 1 respectively, and performing thermal compounding, wherein the thickness of a glue-coated aluminum foil substrate is 6 microns, and the thickness of each conductive glue-coated layer is 2 microns; compounding parameters: the temperature is 160 +/-2 ℃, the pressure is 10t, and the time is 5 s; the thickness of the compounded pole piece is 148 +/-2 um;
s7: and cutting and die cutting the hot compounded pole piece to obtain the negative pole piece with the length and the width of 450 mm and 59 mm.
Comparative example one:
negative electrode wet process formula, hard carbon particles: carbon black super-p: CMC: SBR 94:3: 1.2: 1.8.
cylindrical battery 18650, capacity 1000mAh, its preparation includes the following steps:
manufacturing a wet hard carbon negative plate:
weighing 0.255kg of CMC powder by a 30L planetary mixer, adding into 25.24kg of deionized water, revolving at 20rpm, rotating at 2000rpm, and stirring for 120 min; obtaining glue solution A;
0.638kg of carbon black super-p is weighed and added into the glue solution A, revolution is carried out at 20rpm, and rotation is carried out at 2000rpm, and stirring is carried out for 60 min; obtaining a glue solution B;
weighing 20kg of hard carbon powder, adding into the glue solution B, revolving at 25rpm, rotating at 2500rpm, and stirring for 180 min; obtaining slurry C;
weighing 0.766kg of SBR emulsion with 50% of solid content, weighing 5kg of deionized water, simultaneously adding into the slurry C, revolving at 5rpm, rotating at 500rpm, and stirring for 30 min; obtaining slurry D;
coating and drying the prepared slurry D on a 12-micron aluminum foil on a coating machine at the speed of 10m/min to prepare a coil material with the thickness of 200-240 microns and the surface density of 14.0mg/cm 2;
passing the prepared coil stock through a roller press, controlling the density of the extended pole piece at 7.0mg/cm under the pressure of 30t 2 The thickness of the pole piece is 148 +/-2 um;
and (3) cutting and die cutting the rolled pole piece to obtain the negative pole piece with the length and the width of 450 mm and 59 mm.
Then preparing a positive plate by a traditional wet process, wherein the positive electrode is a Prussian blue material, the gram capacity is 152mAh/g, and the surface density of the positive electrode is 14.0mg/cm 2 The thickness is 182 +/-2 um, the width and the length of the positive electrode sheet are 57mm and 405mm, and the current collector is a 12um aluminum foil.
The membrane is a single layer of PE, 16um in thickness, 61.5mm in width and 1180mm in length. The sodium salt of the electrolyte is sodium hexafluorophosphate with the concentration of 1mol/L, and the solvent is EC, DMC and EMC 1:1: 1.
And winding the wet-process negative plate, the positive electrode and the diaphragm to obtain the winding core of the sodium-ion cylindrical battery. Then the following manufacturing process of the sodium ion cylindrical battery is carried out: putting down an insulating gasket, rolling a core into a shell, rolling a groove on the shell, welding a negative electrode lug with the bottom of the shell, putting up the insulating gasket, laser welding a positive electrode lug and a cap, baking a battery cell, injecting liquid, sealing, standing for 1-2 days, forming, grading and detecting. The sodium ion cell in the comparative example was completed.
And taking the hard carbon pole piece as a positive pole and the sodium piece as a negative pole, carrying out a power-off test, and calibrating the hard carbon gram capacity.
The charging capacity, first efficiency of the full cell, cycle, and EOL cell disassembly interfaces of examples one, two, and one were tested.
Data pairs are as follows:
as can be seen from the above table, in the first example and the second example, compared with the first comparative example, the fresh negative electrode sheet and the EOL electrode sheet in the examples have higher hard carbon gram capacity, lower expansion rate of the electrode sheet, and no material falling after the EOL battery is disassembled. The elastic network formed after the adhesive is fibrillated is shown, the expansion of the negative plate can be well inhibited, meanwhile, the negative pores after charging and discharging are still uniform and regular, more sodium ions can be stably and reversibly adsorbed among the negative pores, the sodium storage amount of the negative electrode is improved, and the battery cycle stability is improved.
The improvement of gram capacity and cycle is more obvious after the proportion of PTFE is increased from 3% to 4% in the first embodiment compared with the second embodiment.
In conclusion, the dry-method negative plate with the elastic network structure can effectively improve gram capacity and cycle of the negative electrode of the sodium-ion battery.
A pure dry sodium ion battery, which comprises a battery cell of the negative plate of the pure dry sodium ion battery in the first embodiment or the second embodiment.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (10)
1. A pure dry method sodium ion battery negative pole which is characterized in that: including current collection body layer (1), electrically conductive rubber coating (2) and fibrillating elastic layer (3), contain electrically conductive rubber coating (2) respectively on the both sides face of current collection body layer (1), two the outside on electrically conductive rubber coating (2) all is provided with fibrillating elastic layer (3), current collection body layer (1), electrically conductive rubber coating (2) and fibrillating elastic layer (3) thermal compound negative pole piece that the lamellar body was described, it contains a plurality of elasticity network structure, and is a plurality of to fibrillate elastic layer (3) the inflation of elasticity network structure suppression negative pole piece.
2. The pure dry method sodium ion battery cathode according to claim 1, characterized in that: the fibrillatable elastic layer (3) comprises a mixture of active substance particles, conductive particles and fibrillatable resin in the form of interlaced fibrils and forming an elastic network.
3. The preparation method of the pure dry method sodium ion battery cathode according to claim 2, characterized in that: dry-mixing active substance particles, conductive particles and fiberizable resin according to the mass part ratio, then fibrillating, and then extruding to prepare the self-supporting base electrode; carrying out multistage calendering and rolling on the base electrode, and then thermally compounding the base electrode with the glued current collector layer to obtain a finished negative plate;
wherein, the mass percentage of the fiberizable resin is 1-5%; the mass percentage of the conductive material is 1-5%; the mass percentage of the active substance particles is 90-98%.
4. The preparation method of the pure dry method sodium ion battery cathode according to claim 3, characterized in that: the active material particles comprise any one or more of hard carbon powder, soft carbon, sulphur, LTO, metal or alloy.
5. The preparation method of the pure dry method sodium ion battery cathode according to claim 3, characterized in that: the conductive particles are any one or more of carbon black super-p, KS-6, conductive graphite, carbon nanotubes, graphene and carbon fibers VGCF.
6. The preparation method of the pure dry method sodium ion battery cathode according to claim 3, characterized in that: the fiberizable resin is PTFE or modified PTFE.
7. The preparation method of the pure dry method sodium ion battery cathode according to claim 3, characterized in that: the active substance particles are hard carbon powder, the conductive particles are carbon black super-p, and the fiberizable resin is modified PTFE; and hard carbon powder: carbon black super-p: the mixing ratio of PTFE in parts by mass is 94:3:3 or 93:3: 4.
8. the preparation method of the pure dry method sodium ion battery cathode according to claim 7, characterized in that: hard carbon powder: carbon black super-p: the mixing ratio of PTFE in parts by mass is 94:3:3 comprises the following preparation steps:
s1: weighing 94 parts by mass of hard carbon powder, wherein D50 is 4um, and adding into a planetary mixer;
s2: weighing 3 parts by mass of carbon black super-p, adding into hard carbon powder, and rotationally stirring for 30min to obtain powder A;
s3: weighing 3 parts by mass of modified PTFE powder with D50 of 0.5-2um, adding into the powder A, and rotationally stirring for 30min to obtain powder B;
s4: fibrillating powder B: fibrillating PTFE with a supersonic gas jet using a jet mill by drawing PTFE at a D50 range of 0.5-2um into filaments having a diameter of 10-100nm and a single length of 5-100um, interlacing the plurality of filaments into an elastic network, and uniformly embedding a hard carbon and carbon black super-p conductive agent in the network;
the mixed powder B after the fibrillation is put into an open mill, and a continuous basic negative plate is extruded from a double roller, the thickness is 100- 2 ；
S5: the basic negative plate smelted in the step S4 is passed through a multi-stage calender, and the density of the extended negative plate is controlled to be 7.0mg/cm 2 The thickness is 70 +/-2 um;
s6: placing two rolls of basic negative plates on the upper and lower surfaces of the glue-coated aluminum foil of the current collector layer respectively, and performing thermal compounding;
s7: and (3) cutting and die-cutting the thermally compounded pole piece to obtain the negative pole piece with the preset width and length.
9. The preparation method of the pure dry method sodium ion battery cathode according to claim 7, characterized in that: hard carbon powder: carbon black super-p: the mixing ratio of PTFE in parts by mass is 93:3:4 comprises the following preparation steps:
s1: weighing 93 parts by mass of hard carbon powder, wherein D50 is 4um, and adding into a planetary stirrer;
s2: weighing 3 parts by mass of carbon black super-p, adding the carbon black super-p into artificial graphite powder, and rotating and stirring for 30min to obtain powder A;
s3: weighing 4 parts by mass of modified PTFE powder, wherein D50 is 0.5-2um, adding into the powder A, and rotating and stirring for 30min to obtain powder B;
s4: fibrillating powder B: fibrillating PTFE with a supersonic gas jet using a jet mill by drawing PTFE at a D50 range of 0.5-2um into filaments having a diameter of 10-100nm and a single length of 5-100um, interlacing the plurality of filaments into an elastic network, and uniformly embedding a hard carbon and carbon black super-p conductive agent in the network;
the mixed powder B after the fibrillation is put into an open mill, and a continuous basic negative plate is extruded from a double roller, the thickness is 100- 2 ；
S5: the basic negative plate smelted in the step S4 passes through a multi-stage calender, and the density of the extended part of the plate is controlled to be 7.0mg/cm 2 The thickness is 70 +/-2 um;
s6: placing two rolls of basic negative plates on the upper and lower surfaces of the glue-coated aluminum foil of the current collector layer respectively, and performing thermal compounding;
s7: and (3) cutting and die-cutting the thermally compounded pole piece to obtain the negative pole piece with the preset width and length.
10. A pure dry method sodium ion battery is characterized in that: a cell comprising the pure dry-process sodium ion battery negative electrode of claim 1.
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