CN116805729B - Composite pole piece preparation method, composite pole piece and lithium battery - Google Patents
Composite pole piece preparation method, composite pole piece and lithium battery Download PDFInfo
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- CN116805729B CN116805729B CN202311057032.0A CN202311057032A CN116805729B CN 116805729 B CN116805729 B CN 116805729B CN 202311057032 A CN202311057032 A CN 202311057032A CN 116805729 B CN116805729 B CN 116805729B
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- negative electrode
- solid electrolyte
- electrode layer
- pole piece
- composite
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- 239000002131 composite material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910052744 lithium Inorganic materials 0.000 title abstract description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 25
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 113
- 239000012528 membrane Substances 0.000 claims abstract description 52
- 239000011800 void material Substances 0.000 claims abstract description 39
- 239000011267 electrode slurry Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000006258 conductive agent Substances 0.000 claims abstract description 15
- 239000007773 negative electrode material Substances 0.000 claims abstract description 14
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- 238000000576 coating method Methods 0.000 claims abstract description 13
- 238000003825 pressing Methods 0.000 claims abstract description 11
- 239000006183 anode active material Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000007493 shaping process Methods 0.000 claims abstract description 8
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- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/043—Processes of manufacture in general involving compressing or compaction
- H01M4/0435—Rolling or calendering
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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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
- 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
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The application provides a composite pole piece preparation method, a composite pole piece and a lithium battery, wherein the method comprises the following steps: uniformly mixing a first negative electrode active material, a first negative electrode binder and a first negative electrode conductive agent to obtain first negative electrode slurry; uniformly mixing a second anode active material, a second anode binder and a second anode conductive agent to obtain second anode slurry; uniformly coating the first negative electrode slurry and the second negative electrode slurry on a negative electrode current collector in sequence, drying and cold pressing; obtaining a negative electrode plate, wherein in the negative electrode plate, the void ratio of the second negative electrode layer is larger than that of the first negative electrode layer; uniformly mixing the solid electrolyte and the binder to obtain a solid electrolyte membrane; the preparation method comprises the steps of carrying out heat treatment on the negative electrode plate and the solid electrolyte membrane, and pressing the negative electrode plate and the solid electrolyte membrane through a shaping roller to obtain the composite electrode plate.
Description
Technical Field
The application relates to the technical field of lithium batteries, in particular to a preparation method of a composite pole piece, the composite pole piece and a lithium battery.
Background
Lithium ion batteries are widely used in portable electric appliances such as mobile phones, notebook computers, digital cameras and the like, and are becoming a secondary battery system with the fastest development speed and the largest sales volume. The existing method for compounding the solid electrolyte on the electrode surface mainly comprises the step of coating the solid electrolyte slurry on the electrode surface in a coating mode, and the wet process is easy to cause pollution and other problems.
At present, an electrode and a solid electrolyte membrane are compounded by a dry process, namely the prepared electrode and the solid electrolyte are directly compounded by rolling, but the problem of insufficient adhesion exists, and the service performance of the battery is affected.
Disclosure of Invention
In order to solve one or more of the above technical problems in the prior art, the embodiment of the application provides a composite pole piece preparation method, a composite pole piece and a lithium battery, so as to solve the problem that the adhesion between the existing electrode and the solid electrolyte is insufficient.
In order to solve the problems, the application provides a preparation method of a composite pole piece, which comprises a current collector, a first negative electrode layer, a second negative electrode layer and a solid electrolyte membrane layer, wherein the first negative electrode layer is arranged between the current collector and the second negative electrode layer, and the second negative electrode layer is arranged between the first negative electrode layer and the solid electrolyte membrane layer;
the method comprises the following steps:
uniformly mixing a first negative electrode active material, a first negative electrode binder and a first negative electrode conductive agent to obtain first negative electrode slurry;
uniformly mixing a second anode active material, a second anode binder and a second anode conductive agent to obtain second anode slurry;
uniformly coating the first negative electrode slurry and the second negative electrode slurry on a current collector in sequence, drying and cold pressing; obtaining a negative electrode plate, wherein in the negative electrode plate, the void ratio of the second negative electrode layer is larger than that of the first negative electrode layer;
uniformly mixing the solid electrolyte and the binder to obtain a solid electrolyte membrane;
and carrying out heat treatment on the negative electrode plate and the solid electrolyte membrane, and pressing the negative electrode plate and the solid electrolyte membrane by a shaping roller to obtain the composite electrode plate.
Further, the first negative electrode layer has a void fraction of 15-40%, and the second negative electrode layer has a void fraction of 20-50%.
Further, the first negative electrode layer has a void ratio of 20 to 35%, and the second negative electrode layer has a void ratio of 25 to 45%.
Further, the temperature of the heat treatment is 60-180 ℃; preferably, the temperature of the heat treatment is 100-180 ℃.
Further, the thickness ratio of the first negative electrode layer to the second negative electrode layer is 1-5:1.
further, the thickness ratio of the first negative electrode layer to the second negative electrode layer is 2-3:1.
further, the solid electrolyte is an inorganic solid electrolyte or a composite electrolyte formed by an inorganic solid electrolyte and a polymer solid electrolyte.
Further, the method further comprises: and preheating the negative electrode plate and the solid electrolyte membrane before heat treatment, wherein the temperature range of the preheating is 60-120 ℃.
In a second aspect, the invention provides a composite pole piece, which is manufactured according to the composite pole piece manufacturing method.
In a third aspect, the present invention provides a lithium ion battery comprising the composite pole piece as described above.
The technical scheme provided by the invention has at least one or more of the following beneficial effects:
in the technical scheme of implementing the invention, the first negative electrode slurry and the second negative electrode slurry are sequentially and uniformly coated on the negative electrode current collector, and are dried and cold-pressed, so that the negative electrode plate with a multi-layer structure is obtained, wherein the void ratio of the second negative electrode layer is larger than that of the first negative electrode layer; the invention ensures the energy density of the battery by arranging a plurality of layers of cathodes with different void ratios, and simultaneously, the second cathode layer with higher void ratio ensures that the cathode pole piece is easier to attach in the thermal compounding process with the solid electrolyte membrane, improves the mechanical property of the dry method for preparing the composite pole piece, and is more beneficial to improving the performance of the battery by arranging a plurality of layers of cathodes with different void ratios.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a block flow diagram of a method for preparing a composite pole piece according to one embodiment of the present invention.
Detailed Description
The void ratio refers to the percentage of void space in the pole piece to the total volume of the pole piece, and is a conventional index of the battery. As described in the background art, in the existing process of compounding an electrode and a solid electrolyte membrane by a dry process, if the gap of a pole layer active material of a negative pole piece is small, although the energy density of a battery can be improved, the lamination space between the pole layer and the solid electrolyte membrane is small, and the bonding degree is insufficient after rolling, so that the pole piece is easy to peel off or crack, and the performance and the service life of the battery are affected; if the gap of the active material of the anode layer of the anode plate is large, the volume energy density of the secondary battery is lost. Aiming at the problems, the application provides a preparation method of a composite pole piece, which can effectively improve the adhesion degree between a negative pole piece and a solid electrolyte membrane on the premise of ensuring the energy density of a battery.
The present application is described in detail below.
The embodiment provides a preparation method of a composite pole piece, the composite pole piece includes a current collector, a first negative electrode layer, a second negative electrode layer and a solid electrolyte layer, wherein the first negative electrode layer is arranged between the current collector and the second negative electrode layer, the second negative electrode layer is arranged between the first negative electrode layer and the solid electrolyte layer, and referring to fig. 1, the specific preparation method includes the following steps:
step S101: uniformly mixing a first negative electrode active material, a first negative electrode binder and a first negative electrode conductive agent to obtain first negative electrode slurry;
the first negative electrode active material includes at least one of graphite, soft carbon, hard carbon, silicon oxide or silicon carbon, and in this embodiment, the first negative electrode active material is graphite. The negative electrode binder is a high molecular compound for adhering the negative electrode active material to the current collector, and has the main functions of binding and maintaining the negative electrode active material, enhancing the contact between the negative electrode active material and the negative electrode conductive agent and between the negative electrode active material and the negative electrode current collector, and better stabilizing the structure of the negative electrode plate. And dispersing and mixing the first negative electrode active material, the first negative electrode binder and the first negative electrode conductive agent according to a certain proportion to obtain first negative electrode slurry.
Step S102: uniformly mixing a second anode active material, a second anode binder and a second anode conductive agent to obtain second anode slurry;
the second negative electrode active material includes at least one of graphite, soft carbon, hard carbon, silicon oxide or silicon carbon, and in this embodiment, the second negative electrode active material is graphite. And dispersing the second anode active material, the second anode binder and the second anode conductive agent in deionized water according to a certain proportion to obtain second anode slurry.
Step S103: uniformly coating the first negative electrode slurry and the second negative electrode slurry on a current collector in sequence, drying and cold pressing; obtaining a negative electrode plate, wherein in the negative electrode plate, the void ratio of the second negative electrode layer is larger than that of the first negative electrode layer;
in a specific embodiment, a copper foil is selected as a current collector of the negative electrode, a first negative electrode slurry and a second negative electrode slurry are sequentially coated on the copper foil, and the copper foil is dried at a high temperature and rolled to form a negative electrode plate.
In a specific embodiment, the porosity can be adjusted by adjusting the active material, for example, by selecting primary particles having a narrow particle size distribution, the porosity can be increased, and by selecting secondary particles to be filled between the primary particles, the porosity can be reduced. The greater the compacted density, the lower the void fraction. For example, if the compacted density of graphite in the second negative electrode layer is less than the compacted density of graphite in the first negative electrode layer, the void fraction of the second negative electrode layer is greater than the void fraction of the first negative electrode layer.
In a specific embodiment, the negative electrode plate is mainly a first negative electrode layer, which has a smaller void ratio and high energy density, so that the battery performance is improved, and the second negative electrode layer has a higher void ratio, and the adhesion force between the negative electrode plate and the solid electrolyte membrane is improved, so that the thickness of the first negative electrode layer can be larger than that of the second negative electrode layer, and the thickness ratio of the first negative electrode layer to the second negative electrode layer is 1-5:1, preferably, the thickness ratio of the first anode layer to the second anode layer is 2 to 3:1.
step S104: uniformly mixing the solid electrolyte and the binder to obtain a solid electrolyte membrane;
in a specific embodiment, the solid electrolyte is an inorganic solid electrolyte or a composite electrolyte formed of an inorganic solid electrolyte and a polymer solid electrolyte.
As a preferred embodiment, the solid electrolyte is a composite electrolyte formed of an inorganic solid electrolyte and a polymer solid electrolyte.
The quality of the binder is not particularly required in the application, the content of the binder is adjusted within the protection scope of the application for the necessary film forming performance, and the content of the binder is 1-15wt percent only as an illustrative example; preferably 3-10wt%; more preferably 5-8wt%.
The electrodeless solid electrolyte comprises one or more of oxide solid electrolyte, sulfide solid electrolyte, halide solid electrolyte, hydride solid electrolyte, boride solid electrolyte and nitride solid electrolyte.
The oxide solid electrolyte comprises one or more garnet ceramics, LISICON-type oxides, NASICON-type oxides, and perovskite-type ceramics. For example, one or more garnet ceramics include, but are not limited to, li 6.5 La 3 Zr 1.75 Te 0.25 O 12 、Li 7 La 3 Zr 2 O 12 、Li 6.2 Ga 0.3 La 2.95 Rb 0.05 Zr 2 O 12 、Li 6.85 La 2.9 Ca 0.1 Zr 1.75 Nb 0.25 O 12 、Li 6.25 Al 0.25 La 3 Zr 2 O 12 、Li 6.75 La 3 Zr 1.75 Nb 0.25 O 12 One or more of the following. One or more LISICON-type oxides include, but are not limited to, li 14 Zn(GeO 4 ) 4 、Li 3+x (P 1−x Si x )O 4 (wherein 0<x<1）、Li 3+x Ge x V 1-x O 4 (wherein 0<x<1) One or more of the following. One or more NASICON type oxides can be selected from LiMM ʹ (PO 4 ) 3 Definition, wherein M and M ʹ are independently selected from Al, ge, ti, sn, hf, zr and La. For example, in certain variations, the one or more NASICON-type oxides include, but are not limited to, li 1+x Al x Ge 2-x (PO 4 ) 3 (LAGP) (wherein 0.ltoreq.x.ltoreq.2), li 1+x Al x Ti 2-x (PO 4 ) 3 (LATP) (where 0.ltoreq.x.ltoreq.2), li 1+ x Y x Zr 2-x (PO 4 ) 3 (LYZP) (wherein 0.ltoreq.x.ltoreq.2), li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 、LiTi 2 (PO 4 ) 3 、LiGeTi(PO 4 ) 3 、LiGe 2 (PO 4 ) 3 、LiHf 2 (PO 4 ) 3 One or more of the following. One or more perovskite-type ceramics including, but not limited to, li 3.3 La 0.53 TiO 3 、LiSr 1.65 Zr 1.3 Ta 1.7 O 9 、Li 2x-y Sr 1-x Ta y Zr 1-y O 3 (wherein x=0.75 y and 0.60<y<0.75）、Li 3/8 Sr 7/16 Nb 3/4 Zr 1/4 O 3 、Li 3x La (2/3-x) TiO 3 (wherein 0<x<0.25 One or more of the following).
Sulfide solid state electrolytes include, but are not limited to, li 2 S-P 2 S 5 、Li 2 S-P 2 S 5 -MS x (wherein M is Si, ge and Sn and 0.ltoreq.x.ltoreq.2), li 3.4 Si 0.4 P 0.6 S 4 、Li 10 GeP 2 S 11.7 O 0.3 、Li 9.6 P 3 S 12 、Li 7 P 3 S 11 、Li 9 P 3 S 9 O 3 、Li 10.35 Si 1.35 P 1.65 S 12 、Li 9.81 Sn 0.81 P 2.19 S 12 、Li 10 (Si 0.5 Ge 0.5 )P 2 S 12 、Li(Ge 0.5 Sn 0.5 )P 2 S 12 、Li(Si 0.5 Sn 0.5 )PsS 12 、Li 10 GeP 2 S 12 （LGPS）、Li 6 PS 5 X (wherein X is Cl, br or I), li 7 P 2 S 8 I、Li 10.35 Ge 1.35 P 1.65 S 12 、Li 3.25 Ge 0.25 P 0.75 S 4 、Li 10 SnP 2 S 12 、Li 10 SiP 2 S 12 、Li 9.54 Si 1.74 P 1.44 S 11.7 C l0.3 、 (1-x) P 2 S 5-x Li 2 S (wherein 0.5.ltoreq.x.ltoreq.0.7).
The halide solid state electrolyte includes, but is not limited to, li 2 CdC l4 、Li 2 MgC l4 、Li 2 Cd I4 、Li 2 ZnI 4 、Li 3 OCl、LiI、Li 5 ZnI 4 、Li 3 OCl 1-x Br x (wherein 0<x<1) One or more of (a) and (b).
Boride solid state electrolytes include, but are not limited to, li 2 B 4 O 7 、Li 2 O-(B 2 O 3 )-(P 2 O 5 ) One or more of (a) and (b).
Nitride solid state electrolytes including but not limited to Li 3 N、Li 7 PN 4 、LiSi 2 N 3 One or more of LiPON.
The hydride solid state electrolyte includes, but is not limited to, li 3 AlH 6 、LiBH 4 、LiBH 4 -LiX (wherein X is one of Cl, br and I), liNH 2 、Li 2 NH、LiBH 4 -LiNH 2 One or more of (a) and (b).
In some embodiments, the inorganic solid state electrolyte may be one or more metal oxide particles or lithium-containing compounds, including but not limited to Al 2 O 3 、SiO 2 、TiO 2 、LiNbO 3 、Li 4 Ti 5 O 4 、Li 3 PO 4 One or more of the following.
A composite solid electrolyte composed of a polymer solid electrolyte and an inorganic solid electrolyte. In the embodiment of the application, the mass ratio of the inorganic solid electrolyte and the polymer solid electrolyte in the composite solid electrolyte is not particularly required, and a user can design according to actual needs. Wherein, the polymer solid electrolyte can be at least one of polyvinyl chloride (PVC), polyacrylonitrile (PAN), polymethyl methacrylate (PMMA) and polyethylene oxide (PEO).
In some embodiments, the lithium salt is included in the polymer solid electrolyte.
In some embodiments, the lithium salt includes, but is not limited to, lithium hexafluorophosphate (LiPF) 6 ) The method comprises the steps of carrying out a first treatment on the surface of the Lithium perchlorate (LiClO) 4 ) Lithium tetrachloroaluminate (LiAlCl) 4 ) Lithium iodide (LiI), lithium bromide (LiBr), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (LiBF) 4 ) Lithium difluorooxalato borate (LiBF) 2 (C 2 O 4 ) (LiODFB), lithium tetraphenylborate (LiB (C) 6 H 5 ) 4 ) Lithium bis (oxalato) borate (LiB (C) 2 O 4 ) 2 ) Lithium tetrafluorooxalate phosphate (LiPF) 4 (C 2 O 4 ) (LiFeP), lithium nitrate (LiNO) 3 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium triflate (LiCF) 3 SO 3 ) Lithium bis (trifluoromethanesulfonyl imide) (LITFSI) (LiN (CF) 3 SO 2 ) 2 ) Lithium bis (fluorosulfonyl imide) (LiN (FSO) 2 ) 2 ) (LIFSI) and combinations thereof. In certain variations, the lithium salt is selected from lithium hexafluorophosphate (LiPF 6 ) Lithium bis (trifluoromethanesulfonyl imide) (LiTFSI) (LiN (CF) 3 SO 2 ) 2 ) Lithium bis (fluorosulfonyl imide) (LiN (FSO) 2 ) 2 ) (LiFSI), lithium fluoroalkylphosphonate (LiFAP), lithium phosphate (Li) 3 PO 4 ) One or more of the following.
Preferably, the polymer solid electrolyte is one or two of PEO and PMMA. PEO and PMMA have lower softening temperature, and can better compound the cathode plate and the solid electrolyte membrane in the hot rolling process.
In some embodiments, the polymer solid electrolyte is present in an amount of 1 to 20wt%; further preferably, the content of the polymer solid electrolyte is 3 to 10wt%.
The content of the lithium salt is not particularly limited in the present application, and adjustment of the content of the lithium salt for the lithium conducting performance of the solid electrolyte membrane is considered to be within the scope of the present application without departing from the inventive concept of the present application.
In some embodiments, the solid electrolyte membrane is formed separately, i.e., the solid electrolyte membrane is formed without the aid of a substrate and the membrane remains intact.
In some embodiments, the side of the solid electrolyte membrane remote from the electrode pads is covered with a substrate having a lower binding force to the solid electrolyte membrane than to the electrode pads. After rolling, at least a portion of the solid electrolyte is transferred to the electrode and separated from the substrate.
It is understood that the preparation process of the negative electrode sheet and the solid electrolyte membrane is independent of the preparation process of the composite electrode.
Step S105: and carrying out heat treatment on the negative electrode plate and the solid electrolyte membrane, and pressing the negative electrode plate and the solid electrolyte membrane by a shaping roller to obtain the composite electrode plate.
The shaping roller can simultaneously have a heating function, and the solid electrolyte membrane and the negative electrode plate are conveyed to a gap between the shaping roller for thermal compounding, so that the composite electrode plate is obtained.
In a specific embodiment, the temperature of the sizing roller is in the range of 60-180 ℃, preferably 100-180 ℃. The proper heating temperature is adjusted, the mechanical capacity of dry preparation is improved, the solid electrolyte membrane and the negative electrode plate can be better attached, the adhesiveness between the negative electrode plate and the solid electrolyte membrane is improved, and the stripping strength of the electrode plate is enhanced.
In a specific embodiment, the anode piece and the solid electrolyte membrane are subjected to preheating treatment before being rolled, the temperature range of the preheating treatment is 60-120 ℃, and the preheated anode piece and the preheated solid electrolyte membrane are softened compared with those before being preheated, so that the ductility of the anode piece and the solid electrolyte membrane is improved; therefore, when the shaping roller rolls the negative pole piece and the solid electrolyte membrane, the heat treatment is more sufficient, the negative pole piece and the solid electrolyte membrane are meshed more tightly, the bonding strength between the negative pole piece and the solid electrolyte membrane is improved, and the composite effect is further improved.
In a specific embodiment, the first negative electrode layer has a void fraction of 15-40% and the second negative electrode layer has a void fraction of 20-50%.
In a specific embodiment, the first negative electrode layer has a void fraction of 20-35% and the second negative electrode layer has a void fraction of 25-45%.
Further preferably, the second negative electrode layer has a void fraction of 35 to 45%.
The embodiment is based on the steps S101-S105, and has the effects of improving the adhesion degree between the negative electrode plate and the solid electrolyte membrane, enhancing the stripping strength of the electrode plate and improving the performance of the battery.
It should be noted that, although the steps are described in the above embodiment in a specific sequential order, it should be understood by those skilled in the art that, in order to achieve the effects of the present invention, different steps need not be performed in such an order, and may be performed simultaneously (in parallel) or in other orders, and these variations are within the scope of the present invention.
Further, the invention also provides a composite pole piece, which is prepared by the preparation method of the composite pole piece according to the steps S101-S105.
Further, the invention provides a lithium ion battery, which comprises the composite pole piece.
It is understood that the battery of the present application may be all solid or semi-solid. When the present application does not contain any more electrolyte than the above-described solid electrolyte structure, the battery of the present application is an all-solid battery. When the present application includes a certain content of a nonaqueous electrolyte or a liquid additive in addition to the above-described solid electrolyte structure, it is a semi-solid battery. The type of the nonaqueous electrolyte and the liquid additive used in the application to the semi-solid battery system is not particularly limited. The nonaqueous electrolytic solution may contain an organic solvent and a lithium salt. The organic solvent herein may use any organic solvent without particular limitation as long as it can serve as a medium through which ions participating in the electrochemical reaction of the battery can move. Specifically, as the organic solvent, ester solvents such as methyl acetate, ethyl acetate, γ -butyrolactone, and epsilon-caprolactone can be used; ether solvents such as dibutyl ether or tetrahydrofuran; ketone solvents, such as cyclohexanone; aromatic hydrocarbon solvents such as benzene and fluorobenzene; carbonate solvents such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (MEC), ethylmethyl carbonate (EMC), ethylene Carbonate (EC) and Propylene Carbonate (PC); alcohol solvents such as ethanol and isopropanol; nitriles such as R-CN (wherein R is a linear, branched or cyclic C2-C20 hydrocarbon group and may contain a double bond aromatic ring or ether linkage); amides such as dimethylformamide; dioxolanes, such as 1, 3-dioxolane; or sulfolane.
Any compound may be used as the lithium salt in the nonaqueous electrolytic solution without particular limitation as long as it can provide lithium ions used in the lithium secondary battery. In particular, lithium hexafluorophosphate) Lithium perchlorate ()>) Lithium tetrachloroaluminate (>) Lithium iodide (LiI), lithium bromide (LiBr), lithium thiocyanate (LiSCN), lithium tetrafluoroborate (++>) Lithium difluorooxalato borate (A)>) (LiODFB), lithium tetraphenylborate (>) Lithium bis (oxalato) borate) (LiBOB), lithium tetrafluorooxalate phosphate (>) (LiFeP), lithium nitrate (>) Lithium hexafluoroarsenate ()>) Lithium triflate (+)>) Bis (trifluoromethanesulfonyl imide) Lithium (LITFSI) process) Lithium bis (fluorosulfonyl) imide (>) (LIFSI) and combinations thereof. In certain variants, the lithium salt is selected from lithium hexafluorophosphate (>) Lithium bis (trifluoromethanesulfonyl imide) (-) -LiTFSI>) Lithium bis (fluorosulfonyl) imide (>) (LiFSI), lithium fluoroalkylphosphonate (LiFAP), lithium phosphate (++>) And combinations thereof, etc. may be used as the lithium salt. The lithium salt may be used at a concentration ranging from 0.1 to 2.0M, such as 0.1M, 0.3M, 0.5M, 0.7M, 0.8M, 1M, 1.2M, 1.3M, 1.5M, 1.6M,1.8M or 2.0M, etc. When the concentration of the lithium salt is within the above range, the electrolyte has suitable conductivity and viscosity, thereby exhibiting excellent performance, and lithium ions can be effectively moved.
The battery described herein further includes a positive electrode, which is not particularly limited, and is generally composed of a positive electrode current collector and a positive electrode active material layer. The positive electrode current collector is generally composed of a conductive metal foil, and illustrative examples include copper foil, aluminum foil, stainless steel, and the like; the positive electrode active material layer is generally composed of a positive electrode active material including but not limited to LiCoO, a conductive agent, and a binder 2 、LiMnO 2 、LiNiO 2 、LiVO 2 、LiNi 1/3 Co 1/3 Mn 1/3 O 2 、LiMn 2 O 4 、LiTi 5 O 12 、Li(Ni 0.5 Mn 1.5 )O 4 、LiFePO 4 、LiMnPO 4 、LiNiPO 4 、LiCoPO 4 、LiNbO 3 Or a sulfur-carbon composite material, or a combination of any one or at least two thereof. Wherein LiCoO 2 、LiMnO 2 、LiNiO 2 、LiVO 2 And LiNi 1/3 Co 1/3 Mn 1/3 O 2 Has a rock salt lamellar structure, liMn 2 O 4 、LiTi 5 O 12 And Li (Ni) 0.5 Mn 1.5 )O 4 Has spinel structure, liFePO 4 、LiMnPO 4 、LiNiPO 4 、LiCoPO 4 And LiNbO 3 Has an olivine structure. Any known positive electrode active material can be used in the present application without departing from the inventive concept of the present application.
The surface of the positive electrode active material may also be coated with a coating layer for the purpose of inhibiting the reaction of the positive electrode active material with the electrolyte or improving the ion transport efficiency of the entire positive electrode.
In some embodiments, the coating of the surface of the positive electrode active material is a solid electrolyte coating, such as lithium lanthanum zirconium oxide, lithium lanthanum titanium oxide, or a combination of a solid electrolyte and a lithium salt, including but not limited to LiPF 6 、LiBF 4 、LiCLO 4 、LiAsF 6 、LiCF 3 SO 3 Or LiN (CF) 3 SO 2 ) 2 One or more of them.
In some embodiments, the outer coating of the positive electrode active material is a ceramic particle coating, such as SiO 2 、Al 2 O 3 、TiO 2 Etc.
In some embodiments, the coating of the surface of the positive electrode active material is a carbon coating, amorphous carbon, graphene, graphite, or the like.
The present application is not particularly limited with respect to the anode active material, the anode binder, and the anode conductive agent in the first anode layer and the second anode layer in the anode, and as an illustrative example, the anode active material may be a lithium-based active material containing, for example, lithium metal and/or a lithium alloy. In certain embodiments, the anode is a silicon-based anode active material comprising silicon, such as a silicon alloy, silicon oxide, or a combination thereof, which in some cases may also be mixed with graphite. In other embodiments, the anode may include a carbonaceous-based anode active material comprising one or more of graphite, graphene, carbon Nanotubes (CNTs), and combinations thereof. In yet other embodiments, the anode includes one or more anode active materials that accept lithium, such as lithium titanium oxide (Li 4 Ti 5 O 12 ) One or more transition metals (e.g., tin (Sn)), one or more metal oxides (e.g., vanadium oxide (V) 2 O 5 ) Tin oxide (SnO), titanium dioxide (TiO) 2 ) Titanium niobium oxide (Ti) x Nb y O z Where 0.ltoreq.x.ltoreq.2, 0.ltoreq.y.ltoreq.24, and 0.ltoreq.z.ltoreq.64), metal alloys (such as copper-tin alloys (Cu) 6 Sn 5 ) And one or more metal sulfides such as iron sulfide (FeS).
Optionally, the positive electrode active material in the positive electrode and the negative electrode active material in the negative electrode may be doped with one or more conductive materials that provide an electron conduction path and/or at least one polymeric binder material that improves the structural integrity of the positive and/or negative electrodes. For example, the anode active material may be optionally doped with a binder such as: poly (tetrafluoroethylene) (PTFE), sodium carboxymethylcellulose (CMC), styrene-butadiene rubber (SBR), polyvinylidene fluoride (PVDF), nitrile-butadiene rubber (NBR), styrene-butylene-styrene copolymer (SEBS), styrene-butadiene-styrene copolymer (SBS), lithium polyacrylate (LiPAA), sodium polyacrylate (NaPAA), sodium alginate, lithium alginate, and combinations thereof. The conductive material may include carbon-based materials, powdered nickel or other metallic particles, or conductive polymers. The carbon-based material may include, for example, particles of carbon black, graphite, superP, acetylene black (such as KETCHENTM black or denktatm black), carbon fibers and nanotubes, graphene, and the like. Examples of the conductive polymer include polyaniline, polythiophene, polyacetylene, polypyrrole, poly (3, 4-ethylenedioxythiophene) polysulfstyrene, and the like.
Embodiments of the present invention will be described more specifically below by way of examples, and the present application and effects will be described in more detail. However, embodiments of the present invention are not limited to these examples only.
Example 1
The embodiment provides a composite pole piece, and the preparation method of the composite pole piece is provided based on the specific embodiment:
1. preparing a negative electrode plate:
(1) Graphite, carbon nanotubes and binder were mixed according to a ratio of 95:2:3, performing dispersion mixing to obtain first negative electrode slurry;
(2) Dispersing graphite, carbon nano tubes and a binder in deionized water to obtain second negative electrode slurry;
wherein the compacted density of graphite in the first negative electrode layer is 1.2g/cm 3 The compacted density of graphite in the second negative electrode layer was 1.0g/cm 3 ；
And sequentially coating a first negative electrode slurry and a second negative electrode slurry on a negative electrode current collector copper foil, drying at 120 ℃, and rolling to form a negative electrode plate, wherein the void ratio of the first negative electrode layer is 32.1%, and the void ratio of the second negative electrode layer is 41.8%.
2. Preparing a solid electrolyte membrane:
LLZO is selected as a solid electrolyte, polytetrafluoroethylene is used as a binder, the binder content is 8wt%, and the solid electrolyte mixture is obtained by mixing the materials and stirring the materials by using a high-speed stirrer. And then carrying out fiberization treatment on the mixture by an air flow mill to obtain a fiberized solid electrolyte mixture, and pressing the fiberized solid electrolyte mixture by a roller to obtain the solid electrolyte membrane.
3. Preparing a composite pole piece:
and conveying the solid electrolyte membrane and the negative electrode plate to a gap between shaping rollers for rolling and thermal compounding to obtain a composite electrode plate, wherein the heating temperature is 60 ℃ in the thermal compounding process.
Example 2
The difference between this example and example 1 is that the first negative electrode layer in this example has a porosity of 32.5% and the second negative electrode layer has a porosity of 41.9%, and the heating temperature during thermal compounding is 80 ℃.
The remaining preparation methods, parameters were identical to those of example 1.
Example 3
The difference between this example and example 1 is that in this example, the first negative electrode layer has a porosity of 33.6% and the second negative electrode layer has a porosity of 42.6%, and the heating temperature is 100 ℃ during the thermal compounding process.
The remaining preparation methods, parameters were identical to those of example 1.
Example 4
This example differs from example 1 in that LLZO and PEO are used as solid electrolytes, liPF 6 As the lithium salt, wherein the content of the binder was 8wt%, the content of PEO was 10wt%, and the content of the lithium salt was 2wt%. In this example, the first negative electrode layer had a porosity of 33.6%, the second negative electrode layer had a porosity of 42.6%, and the heating temperature was 120 ℃.
The remaining preparation methods, parameters were identical to those of example 1.
Example 5
The difference between this example and example 1 is that LLZO and PMMA are used as solid electrolyte, liPF 6 As a lithium salt, the first negative electrode layer in this example had a void fraction of 32.3%, and the second negative electrode layer had a void fraction of 41.5In the thermal compounding process, the heating temperature is 60 ℃.
The remaining preparation methods, parameters were identical to those of example 4.
Example 6
The difference between this example and example 1 is that LLZO and PMMA are used as solid electrolyte, liPF 6 As the lithium salt, the first negative electrode layer in this example had a porosity of 32.3%, and the second negative electrode layer had a porosity of 41.5%, and the heating temperature was 120 ℃ during the thermal compounding.
The remaining preparation methods, parameters were identical to those of example 4.
Example 7
The difference between this example and example 1 is that LLZO and PAN are used as solid electrolytes, and LiPF 6 As the lithium salt, the first negative electrode layer in this example had a porosity of 32.8%, and the second negative electrode layer had a porosity of 38.8%, and the heating temperature was 120 ℃ during the thermal compounding.
The remaining preparation methods, parameters were identical to those of example 4.
Example 8
The difference between this example and example 6 is that LLZO and PMMA are used as solid electrolyte, liPF 6 As lithium salt, step 3 in this example preheats the anode tab and the solid electrolyte membrane at 120 ℃ before thermal compounding.
The remaining preparation methods, parameters were identical to those of example 6.
Comparative example 1
The difference between this comparative example and example 1 is that the first negative electrode layer has a void fraction of 41.8% and the second negative electrode layer has a void fraction of 32.6%.
The remaining preparation methods, parameters were identical to those of example 1.
Comparative example 2
The difference between this comparative example and example 1 is that the negative electrode sheet in this comparative example is only one layer, and the first negative electrode layer is taken as the negative electrode sheet, i.e., the void fraction of the negative electrode sheet is 37.8%.
The preparation process and parameters were identical to those of steps 2 and 3 of example 1.
Preparation of the positive electrode of the above examples and comparative examples:
according to the positive electrode active material, the conductive agent and the binder according to 95:3:2, performing dispersion mixing to form positive electrode slurry coating and current collector aluminum foil, and drying and cold pressing to obtain a positive electrode plate.
Wherein the positive electrode active material is LiCoO2, the conductive agent is super-P, and the binder is PVDF.
Preparation of the battery:
and preparing electrolyte with the concentration of lithium salt of LiPF6 and the concentration of lithium salt of 1mol/L by using EC: PC=1:1, assembling the positive electrode, the negative electrode and the diaphragm prepared by the method into a battery, injecting the electrolyte, standing and forming to obtain the lithium ion battery.
The testing method comprises the following steps:
1. peel strength test:
the composite pole piece prepared in the above way is subjected to peel strength performance test according to the following method, wherein the test method comprises the following steps:
(1) firstly, cutting the composite pole piece into long strips with the length of 170mm and the width of 20mm respectively by using a flat paper cutter, and wiping the steel plate ruler without scales by using dust-free paper without leaving stains and dust;
(2) secondly, sticking double-sided adhesive tape with the width of 25mm on a steel plate ruler without graduation, wherein the length is 70mm, and the position is centered;
(3) then, sticking the test sample on a double-sided adhesive tape, enabling the end surfaces to be flush, and rolling the test sample back and forth on the surface of the composite pole piece for 3 times by using a pressing wheel (2 kg) with the diameter of 84mm and the height of 45 mm;
(4) and after the free end of the composite pole piece in the experimental sample is turned over by 180 degrees, the composite pole piece is clamped on an upper clamp of a tensile force tester, a non-scale steel plate ruler is clamped on a lower clamp, the stretching speed of the pole piece is set to be 200mm/min, the average value of stretching 25-80 mm (total stretching distance is 100 mm) is measured, the composite pole piece is stripped, and when the negative pole piece and the solid electrolyte membrane are completely separated, the test result of the stripping strength is read.
2. The normal temperature cycle test method comprises the following steps:
(1) charging at normal temperature with 1C or prescribed current to a final voltage, cutting off the current by 0.05C, and standing for 30min;
(2) discharging at 1C to discharge final pressure, recording discharge capacity, and standing for 30min;
(3) and (3) circulating the steps (1) - (2).
The results of the performance test of the composite pole pieces prepared in examples 1 to 6 and comparative examples 1 to 2 are shown in Table 1.
Table 1 results of performance testing of composite pole pieces
From the test results of table 1, it can be seen that:
it is known in the art that too large a void fraction directly affects the energy density, and if too small, although the energy density can be improved, the performance of the battery is affected, the binding force of the negative electrode tab and the solid electrolyte membrane is weakened, the peel strength is lowered, and the cycle performance of the battery is lowered.
This application has both guaranteed energy density through setting up the negative pole that the multilayer has different void fractions, simultaneously, carries out the complex with solid electrolyte membrane under the higher roll-in temperature of the higher second negative pole layer cooperation of void fraction, has improved the mechanical properties of dry process preparation composite pole piece, and the higher void fraction of second negative pole layer more is favorable to improving the performance of battery.
Comparing examples 1-3 and 7, it is known that when the porosity of the second negative electrode layer is higher, the mechanical properties and the battery performance of the composite pole piece are improved by matching with high-temperature rolling, and when the porosity of the second negative electrode layer is smaller, even if the rolling temperature is increased, the improvement on the battery performance is limited; from comparison of examples 4-7, it is known that the solid electrolyte membrane adopts a composite electrolyte formed by inorganic solid electrolyte and polymer solid electrolyte, wherein the polymer solid electrolyte adopts PEO and PMMA, the softening temperature is lower, the negative electrode pole piece and the solid electrolyte membrane can be better compounded in the hot rolling process, the mechanical property and the battery performance of the composite pole piece are improved, and the performance of the composite pole piece without the polymer solid electrolyte along with the temperature rise is improved less than that of the composite pole piece with the polymer solid electrolyte. From examples 6 and 8, it can be seen that the preheating treatment of the pole piece and the solid electrolyte membrane can make the heat treatment more sufficient, and is beneficial to the improvement of the mechanical property and the battery performance of the composite pole piece.
The foregoing description of the preferred embodiments of the present application is not intended to limit the invention to the particular embodiments of the present application, but to limit the scope of the invention to the particular embodiments of the present application.
Claims (5)
1. A preparation method of a composite pole piece is characterized in that,
the composite pole piece comprises a current collector, a first negative electrode layer, a second negative electrode layer and a solid electrolyte membrane layer, wherein the first negative electrode layer is arranged between the current collector and the second negative electrode layer, and the second negative electrode layer is arranged between the first negative electrode layer and the solid electrolyte membrane layer;
the method comprises the following steps:
uniformly mixing a first negative electrode active material, a first negative electrode binder and a first negative electrode conductive agent to obtain first negative electrode slurry;
uniformly mixing a second anode active material, a second anode binder and a second anode conductive agent to obtain second anode slurry;
uniformly coating the first negative electrode slurry and the second negative electrode slurry on a current collector in sequence, drying and cold pressing; obtaining a negative electrode plate, wherein in the negative electrode plate, the void ratio of the second negative electrode layer is larger than that of the first negative electrode layer;
uniformly mixing the solid electrolyte and the binder to obtain a solid electrolyte membrane;
carrying out heat treatment on the negative electrode plate and the solid electrolyte membrane, and pressing the negative electrode plate and the solid electrolyte membrane through a shaping roller to obtain a composite electrode plate;
the first negative electrode layer has a void ratio of 15-40%, and the second negative electrode layer has a void ratio of 20-50%;
the temperature of the heat treatment is 60-180 ℃;
the method further comprises the steps of: preheating the negative electrode plate and the solid electrolyte membrane before heat treatment, wherein the temperature range of the preheating is 60-120 ℃;
the thickness ratio of the first negative electrode layer to the second negative electrode layer is 2-3:1.
2. the method of manufacturing a composite electrode sheet according to claim 1, wherein the first negative electrode layer has a void fraction of 20 to 35% and the second negative electrode layer has a void fraction of 25 to 45%.
3. The method for preparing a composite electrode sheet according to claim 1, wherein the solid electrolyte is an inorganic solid electrolyte or a composite electrolyte formed by an inorganic solid electrolyte and a polymer solid electrolyte.
4. A composite pole piece, characterized in that it is produced by the composite pole piece production method according to any one of claims 1 to 3.
5. A lithium ion battery comprising the composite pole piece of claim 4.
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