CN117637988A - Negative electrode plate of high-energy-density battery, preparation method of negative electrode plate, battery and power utilization device - Google Patents
Negative electrode plate of high-energy-density battery, preparation method of negative electrode plate, battery and power utilization device Download PDFInfo
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- CN117637988A CN117637988A CN202311687449.5A CN202311687449A CN117637988A CN 117637988 A CN117637988 A CN 117637988A CN 202311687449 A CN202311687449 A CN 202311687449A CN 117637988 A CN117637988 A CN 117637988A
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- negative electrode
- electrode plate
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- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 27
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 26
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- 239000000463 material Substances 0.000 claims description 7
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- 239000002041 carbon nanotube Substances 0.000 claims description 6
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- 229910021389 graphene Inorganic materials 0.000 claims description 6
- -1 lithium hexafluorophosphate lithium salt Chemical compound 0.000 claims description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 6
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 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 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 4
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 4
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- 239000007774 positive electrode material Substances 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 2
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical compound [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
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- GBCAVSYHPPARHX-UHFFFAOYSA-M n'-cyclohexyl-n-[2-(4-methylmorpholin-4-ium-4-yl)ethyl]methanediimine;4-methylbenzenesulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1.C1CCCCC1N=C=NCC[N+]1(C)CCOCC1 GBCAVSYHPPARHX-UHFFFAOYSA-M 0.000 description 1
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Classifications
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- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of batteries, in particular to a negative electrode plate of a high-energy-density battery, a preparation method of the negative electrode plate, the battery and an electric device. The negative electrode plate of the high-energy-density battery comprises a current collector and a conductive layer arranged on at least one side of the current collector, wherein the conductive layer comprises a conductive agent, a thickening agent and a binder, the conductive agent comprises a carbon material and is used for uniformly depositing sodium ions or lithium ions, the protective layer is arranged on the surface of the conductive layer, and the protective layer comprises an inorganic filler and an organic polymer and is used for reducing the generation of dendrites and reducing the risk of short circuit of the battery; the negative electrode plate of the high-energy-density battery does not have a negative electrode active material layer, so that the thickness of the negative electrode plate of the high-energy-density battery is reduced, the cost is reduced, and the volume energy density and the weight energy density of the battery are improved.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a negative electrode plate of a high-energy-density battery, a preparation method of the negative electrode plate, the battery and an electric device.
Background
Since the development of ion battery technology, lithium ion batteries are relatively mature in industrialization. However, the crust content of lithium element is very low, and in recent years, along with the mass application of lithium ion batteries in the electric vehicle field and the energy storage field, the limitation of lithium resource shortage is more obvious, the price of the main raw material lithium carbonate of the lithium ion batteries is greatly increased, so that the production cost of industrial chain enterprises is also greatly increased, and the development of the lithium ion batteries is seriously influenced and restricted. Sodium ion batteries are again being focused and studied by the industry because of their abundant raw material resources and low and stable price.
The energy density of the sodium ion battery is lower than that of the lithium ion battery, the energy density of the lithium ion battery adopting lithium iron phosphate can be 350wh/L (the energy density of the lithium ion battery adopting ternary materials is higher and can reach about 680 wh/L), the energy density of the sodium ion battery adopting O3 phase layered oxide with the highest energy density can only reach about 270-300wh/L, and the energy density of the sodium ion battery is lower than that of the lithium ion battery by about 20% -30%, so that the application of the sodium ion battery is limited by the lower energy density.
Disclosure of Invention
The invention mainly aims to provide a negative electrode plate of a high-energy-density battery, which improves the energy density of the battery.
In order to achieve the above object, the negative electrode piece of the high-energy-density battery provided by the invention comprises a current collector, a conductive layer arranged on at least one side of the current collector, and a protective layer arranged on the surface of the conductive layer, wherein the conductive layer comprises a conductive agent, a thickening agent and a binder, the conductive agent comprises a carbon material, and the protective layer comprises an inorganic filler and an organic polymer.
The negative electrode plate of the high-energy-density battery does not have a negative electrode active material layer, and metal ions are deposited on the negative electrode in a metal deposition mode. The negative electrode plate of the high-energy-density battery comprises a current collector and a conductive layer arranged on at least one side of the current collector, wherein the conductive layer comprises a carbon material for uniformly depositing sodium ions or lithium ions, the protective layer is arranged on the surface of the conductive layer, and the protective layer comprises an inorganic filler for reducing the generation of dendrites and reducing the risk of short circuit of the battery; the negative electrode plate of the high-energy-density battery does not have a negative electrode active material layer, so that the thickness of the negative electrode plate of the high-energy-density battery is reduced, the cost is reduced, and the volume energy density and the weight energy density of the battery are improved.
Optionally, the conductive layer has a thickness of 1 μm to 20 μm;
and/or the particle diameter D50 of the conductive agent ranges from 5nm to 1 μm;
the thickness of the conductive layer in the above range can improve uniformity of metal deposition.
The particle size of the conductive agent is in the above range, which is conducive to the preparation of the conductive layer of the above thickness, and the uniform deposition of the metal, that is, the particle size is conducive to the formation of the uniform conductive layer, and the cycle performance of the battery is improved.
Optionally, the mass part ratio of the conductive agent, the thickener and the binder is (2-20 parts): (0 to 3 parts): (2-8 parts).
Optionally, the conductive agent comprises at least one of carbon black, carbon nanotubes, graphene;
and/or the thickener comprises at least one of carboxymethyl cellulose, polyethylene oxide and polyacrylate;
and/or the binder comprises at least one of styrene-butadiene rubber, polyacrylate, polyethylene oxide and polyvinylidene fluoride.
The conductive agent in the application comprises at least one of carbon black, carbon nano tube and graphene; the thickener in the present application includes, but is not limited to, at least one of carboxymethyl cellulose, polyethylene oxide, polyacrylate; the binder in the present application includes, but is not limited to, at least one of styrene-butadiene rubber, polyacrylate, polyethylene oxide, polyvinylidene fluoride.
Optionally, the mass fraction ratio of the inorganic filler to the organic polymer is (1 to 10 parts): (1-10 parts).
The protective layer comprises an organic polymer, the protective layer formed by the organic polymer has the characteristics of porosity and elasticity, the porosity can enable metal ions to quickly pass through the protective layer, the protective layer can be extruded in the expansion process of the negative electrode plate due to the elastic characteristics, the problem of battery expansion is relieved, and meanwhile, the protective layer has the characteristics of microcosmic conduction of ions and macroscopic inhibition of dendrite penetration.
Optionally, the thickness of the protective layer is 1 μm to 20 μm;
and/or the current collector comprises aluminum foil, copper foil, stainless steel foil, nickel foil;
and/or the particle diameter D50 of the inorganic filler ranges from 1nm to 1 μm.
The thickness of the protective layer is in the range, so that the risk of short circuit caused by dendrite can be reduced, the protective layer is in the range, the gap formed between the pole pieces is reduced in the process of shrinking the cathode, the problem that the pole piece gap is enlarged, the ion transmission performance is poor and the battery cycle performance is poor is solved.
It can be understood that the organic polymer in the protective layer expands in volume after absorbing the electrolyte, so that before the bare cell is assembled into the battery shell, the thickness of the bare cell is smaller than the inner thickness of the shell, so that the bare cell can be conveniently assembled, and after the electrolyte is injected, the protective layer in the bare cell expands, so that the bare cell is tightly contacted with the inner wall of the battery shell, and the cycle performance of the battery cell is improved. The organic polymer comprises one or more of PAN (polyacrylonitrile), PEO (polyethylene oxide), PVDF (polyvinylidene fluoride) and polyacrylic resin.
Current collectors include, but are not limited to, aluminum foil, copper foil, stainless steel foil, nickel foil.
The particle size of the inorganic filler is in the above range, and the structural strength of the protective layer, as well as the ability to pass ions, can be improved.
Optionally, the inorganic filler comprises at least one of fumed silica, nano-alumina, boehmite;
and/or the organic polymer comprises at least one of polyvinylidene fluoride, polymethyl methacrylate, polyimide and polyethylene oxide.
Inorganic fillers of the present application include, but are not limited to, at least one of fumed silica, nano-alumina, boehmite; the organic polymer of the present application includes, but is not limited to, at least one of polyvinylidene fluoride, polymethyl methacrylate, polyimide, polyethylene oxide.
It is also understood that a solid electrolyte may also be added to the protective layer.
Optionally, the present application further provides a method for preparing the negative electrode plate of the high energy density battery, which includes:
preparing conductive agent slurry and protective layer slurry, and coating the conductive agent slurry and the protective layer slurry on at least one side of a current collector in a double-layer manner to obtain a negative electrode plate of the high-energy-density battery;
in the step of preparing the conductive agent paste and the protective layer paste, the steps of:
preparing a conductive agent, a thickener, a binder and a solvent, wherein the mass ratio of the conductive agent to the thickener to the binder to the solvent is 2-20): (0 to 3 parts): (2-8 parts): (80-180 parts) dissolving the thickener into a solvent, stirring, adding the conductive agent, dispersing, adding the binder, and dispersing to obtain the conductive agent slurry;
preparing an inorganic filler, an organic polymer and an organic solvent, wherein the mass ratio of the inorganic filler to the organic polymer to the organic solvent is (1-10): (1-10 parts): and (40-100 parts) dissolving the organic polymer into the organic solvent to form a mixed solution, adding the inorganic filler into the mixed solution, and dispersing to obtain the protective layer slurry.
The present application also provides a battery comprising an electrolyte, a positive electrode sheet, and a negative electrode sheet of the high energy density battery of claim;
or the battery comprises electrolyte and the negative electrode plate of the high-energy-density battery, which is obtained by the preparation method of the negative electrode plate of the high-energy-density battery;
the electrolyte is applied to a lithium ion battery and comprises lithium hexafluorophosphate lithium salt and one or more of dimethyl carbonate, ethylene carbonate, ethylmethyl carbonate, diethyl carbonate and propylene carbonate;
the electrolyte is applied to sodium ion batteries and comprises sodium hexafluorophosphate sodium salt and one or more of dimethyl carbonate, ethylene carbonate, methyl ethyl carbonate, diethyl carbonate and propylene carbonate;
the positive electrode plate is applied to a sodium ion battery and comprises at least one of sodium-containing layered oxide and polyanion sodium salt;
the positive pole piece is applied to a lithium ion battery and comprises at least one of lithium cobaltate, lithium ternary material, lithium manganate, lithium iron phosphate and lithium manganese iron phosphate;
the battery outer package comprises an aluminum-plastic composite film, a steel shell, an aluminum shell and a plastic shell;
the shape of the battery includes square and cylindrical.
Optionally, the application further provides an electric device comprising a battery as described.
The application provides a negative electrode plate of a high-energy-density battery, which comprises a current collector and a conductive layer arranged on at least one side of the current collector, wherein the conductive layer comprises a conductive agent, a thickening agent and a binder, the conductive agent comprises a carbon material and is used for uniformly depositing sodium ions or lithium ions, the protective layer is arranged on the surface of the conductive layer, and the protective layer comprises an inorganic filler and an organic polymer and is used for reducing the generation of dendrites and reducing the risk of short circuit of the battery; the negative electrode plate of the high-energy-density battery does not have a negative electrode active material layer, so that the thickness of the negative electrode plate of the high-energy-density battery is reduced, the cost is reduced, and the volume energy density and the weight energy density of the battery are improved.
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 required in the embodiments or the description of the prior art will be briefly described, 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 the structures shown in these drawings without inventive effort for a person skilled in the art.
Fig. 1 is a schematic structural view of a negative electrode tab of a high energy density battery according to the present invention.
Reference numerals illustrate:
the achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It should be noted that all directional indicators (such as up, down, left, right, front, and rear … …) in the embodiments of the present invention are merely used to explain the relative positional relationship, movement, etc. between the components in a particular posture (as shown in the drawings), and if the particular posture is changed, the directional indicator is changed accordingly.
In the present invention, unless specifically stated and limited otherwise, the terms "connected," "affixed," and the like are to be construed broadly, and for example, "affixed" may be a fixed connection, a removable connection, or an integral body; can be mechanically or electrically connected; either directly or indirectly, through intermediaries, or both, may be in communication with each other or in interaction with each other, unless expressly defined otherwise. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
Furthermore, descriptions such as those referred to as "first," "second," and the like, are provided for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implying an order of magnitude of the indicated technical features in the present disclosure. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In addition, the meaning of "and/or" as it appears throughout is meant to include three side-by-side schemes, for example, "a and/or B", including a scheme, or B scheme, or a scheme that is satisfied by both a and B. In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The energy density of the sodium ion battery is lower than that of the lithium ion battery, the energy density of the lithium ion battery adopting lithium iron phosphate can be 350wh/L (the energy density of the lithium ion battery adopting ternary materials is higher and can reach about 680 wh/L), the energy density of the sodium ion battery adopting O3 phase layered oxide with the highest energy density can only reach about 270-300wh/L, and the energy density of the sodium ion battery is lower than that of the lithium ion battery by about 20% -30%, so that the application of the sodium ion battery is limited by the lower energy density.
In order to solve the technical problems, the application provides a negative electrode plate of a high-energy-density battery, which improves the energy density of the battery.
The negative electrode plate of the high-energy-density battery comprises a current collector, a conductive layer arranged on at least one side of the current collector and a protective layer arranged on the surface of the conductive layer, wherein the conductive layer comprises a conductive agent, a thickening agent and a binder, the conductive agent comprises a carbon material, and the protective layer comprises an inorganic filler and an organic polymer.
As shown in fig. 1, a negative electrode tab 100 of a high energy density battery according to an embodiment includes a current collector 10, and a conductive layer 20 and a protective layer 30 disposed on the current collector 10.
The negative electrode plate of the high-energy-density battery does not have a negative electrode active material layer, and metal ions are deposited on the negative electrode in a metal deposition mode. The negative electrode plate of the high-energy-density battery comprises a current collector and a conductive layer arranged on at least one side of the current collector, wherein the conductive layer comprises a carbon material for uniformly depositing sodium ions or lithium ions, the protective layer is arranged on the surface of the conductive layer, and the protective layer comprises an inorganic filler for reducing the generation of dendrites and reducing the risk of short circuit of the battery; the negative electrode plate of the high-energy-density battery does not have a negative electrode active material layer, so that the thickness of the negative electrode plate of the high-energy-density battery is reduced, the cost is reduced, and the volume energy density and the weight energy density of the battery are improved.
Optionally, the conductive layer has a thickness of 1 μm to 20 μm; and/or the particle diameter D50 of the conductive agent ranges from 5nm to 1 μm.
The thickness of the conductive layer in the above range can improve uniformity of metal deposition.
The particle size of the conductive agent is in the above range, which is conducive to the preparation of the conductive layer of the above thickness, and the uniform deposition of the metal, that is, the particle size is conducive to the formation of the uniform conductive layer, and the cycle performance of the battery is improved.
The values of 1 μm to 20 μm described above include the minimum value and the maximum value of the range, and each value between such minimum value and maximum value, and specific examples include, but are not limited to, dot values in the examples and range values between 1 μm, 2 μm, 5 μm, 10 μm, 12 μm, 14 μm, 16 μm, 18 μm, 20 μm, and the like, and any two of the dot values described above.
In one embodiment, the mass part ratio range of the conductive agent, the thickener and the binder is (2-20): (0 to 3 parts): (2-8 parts).
In an embodiment, the conductive agent includes at least one of carbon black, carbon nanotubes, graphene; and/or the thickener comprises at least one of carboxymethyl cellulose, polyethylene oxide and polyacrylate; and/or the binder comprises at least one of styrene-butadiene rubber, polyacrylate, polyethylene oxide and polyvinylidene fluoride.
The conductive agent in the application comprises at least one of carbon black, carbon nano tube and graphene; the thickener in the present application includes, but is not limited to, at least one of carboxymethyl cellulose, polyethylene oxide, polyacrylate; the binder in the present application includes, but is not limited to, at least one of styrene-butadiene rubber, polyacrylate, polyethylene oxide, polyvinylidene fluoride.
In one embodiment, the mass fraction ratio of the inorganic filler to the organic polymer ranges from 1 part to 10 parts: (1-10 parts).
The protective layer comprises an organic polymer, the protective layer formed by the organic polymer has the characteristics of porosity and elasticity, the porosity can enable metal ions to quickly pass through the protective layer, the protective layer can be extruded in the expansion process of the negative electrode plate due to the elastic characteristics, the problem of battery expansion is relieved, and meanwhile, the protective layer has the characteristics of microcosmic conduction of ions and macroscopic inhibition of dendrite penetration.
In one embodiment, the protective layer has a thickness of 1 μm to 20 μm; and/or the current collector comprises aluminum foil, copper foil, stainless steel foil, nickel foil; and/or the particle diameter D50 of the inorganic filler ranges from 1nm to 1 μm.
The thickness of the protective layer is in the range, so that the risk of short circuit caused by dendrite can be reduced, the protective layer is in the range, the gap formed between the pole pieces is reduced in the process of shrinking the cathode, the problem that the pole piece gap is enlarged, the ion transmission performance is poor and the battery cycle performance is poor is solved.
It can be further understood that the organic polymer in the protective layer expands in volume after absorbing the electrolyte, so that before the bare cell is assembled into the battery shell, the thickness of the bare cell is smaller than the inner thickness of the shell, so that the bare cell can be conveniently assembled, and after the electrolyte is injected, the protective layer in the bare cell expands, so that gaps between the bare cell and the inner wall of the battery shell are tightly contacted, and the cycle performance of the battery cell is improved. The organic polymer comprises one or more of PAN (polyacrylonitrile), PEO (polyethylene oxide), PVDF (polyvinylidene fluoride) and polyacrylic resin.
Current collectors include, but are not limited to, aluminum foil, copper foil, stainless steel foil, nickel foil.
The particle size of the inorganic filler is in the above range, and the structural strength of the protective layer, as well as the ability to pass ions, can be improved.
In one embodiment, the inorganic filler comprises at least one of fumed silica, nano-alumina, boehmite; and/or the organic polymer comprises at least one of polyvinylidene fluoride, polymethyl methacrylate, polyimide and polyethylene oxide.
Inorganic fillers of the present application include, but are not limited to, at least one of fumed silica, nano-alumina, boehmite; the organic polymer of the present application includes, but is not limited to, at least one of polyvinylidene fluoride, polymethyl methacrylate, polyimide, polyethylene oxide.
It is also understood that a solid electrolyte may also be added to the protective layer.
In an embodiment, the present application further provides a method for preparing a negative electrode sheet of a high energy density battery, including: preparing conductive agent slurry and protective layer slurry, and coating the conductive agent slurry and the protective layer slurry on at least one side of a current collector in a double-layer manner to obtain a negative electrode plate of the high-energy-density battery; in the step of preparing the conductive agent paste and the protective layer paste, the steps of: preparing a conductive agent, a thickening agent, a binder and a solvent, wherein the mass parts of the conductive agent, the thickening agent, the binder and the solvent are (2-20): (0 to 3 parts): (2-8 parts): (80-180 parts) dissolving a thickening agent into a solvent, stirring, adding a conductive agent, dispersing, adding a binder, and dispersing to obtain a conductive agent slurry; preparing inorganic filler, organic polymer and organic solvent, wherein the mass ratio of the inorganic filler to the organic polymer to the organic solvent is (1-10): (1-10 parts): (40-100 parts), dissolving an organic polymer into an organic solvent to form a mixed solution, adding an inorganic filler into the mixed solution, and dispersing to obtain the protective layer slurry.
The application also provides a battery, which comprises electrolyte, an anode plate and a cathode plate of the high-energy-density battery; or the battery comprises electrolyte and the negative electrode plate of the high-energy-density battery obtained by the preparation method of the negative electrode plate of the high-energy-density battery; the electrolyte is applied to a lithium ion battery and comprises lithium hexafluorophosphate lithium salt and one or more of dimethyl carbonate, ethylene carbonate, ethylmethyl carbonate, diethyl carbonate and propylene carbonate; the electrolyte is applied to sodium ion batteries and comprises sodium hexafluorophosphate sodium salt and one or more of dimethyl carbonate, ethylene carbonate, methyl ethyl carbonate, diethyl carbonate and propylene carbonate; the positive electrode plate is applied to a sodium ion battery and comprises at least one of sodium-containing layered oxide and polyanion sodium salt; the positive pole piece is applied to a lithium ion battery and comprises at least one of lithium cobaltate, lithium ternary material, lithium manganate, lithium iron phosphate and lithium manganese iron phosphate; the battery outer package comprises an aluminum-plastic composite film, a steel shell, an aluminum shell and a plastic shell; the shape of the battery includes square and cylindrical shapes.
For example, a method of making a battery: the preparation method comprises the steps of (1) preparing a positive electrode material, namely dissolving a layered oxide of a sodium ion battery positive electrode material, conductive carbon black, PVDF and NMP in a prescribed proportion, dissolving the PVDF in the NMP to form a clear and transparent solution, adding the carbon black, dispersing for 2 hours at a high speed to form a uniform dispersion liquid, adding a positive electrode active material, and stirring for 3 hours at a high speed to form a uniform positive electrode slurry; coating, namely using aluminum foil as a positive electrode current collector, coating a positive electrode on the aluminum foil according to a set surface density, and drying to obtain a positive electrode of the sodium ion battery; rolling and slitting, namely pressing the positive electrode plate to a specified thickness through a roller press, so that particles of the positive electrode material are in closer contact with each other, and the conductivity is better; and manufacturing the positive plate with a specified shape by using a punching or cutting method. Preparing a negative electrode conductive paste, namely dissolving carbon black (conductive agent), CMC (thickener), SBR (binder) and water into water according to a specified proportion, stirring to obtain a clear solution, adding the carbon black, uniformly dispersing, then adding the SBR, and further uniformly dispersing; coating the prepared conductive paste on an aluminum current collector uniformly according to a specified thickness, and drying; preparing a negative electrode protective layer, namely dissolving fumed silica (inorganic filler), PVDF (organic polymer) and NMP into NMP according to a specified proportion to form a clear solution, and then adding the fumed silica into the solution to be uniformly dispersed; secondary coating, namely uniformly coating the negative electrode protection glue solution on the aluminum current collector coated with the conductive paste according to a specified thickness, and drying to form a negative electrode plate of the high-energy-density battery; cutting, namely manufacturing the negative electrode plate of the high-energy-density battery coated with the protection glue solution into the negative electrode plate of the high-energy-density battery according to the specified size. Assembling, namely stacking or winding the positive pole piece, the diaphragm and the negative pole piece of the high-energy-density battery in sequence to form a core body of the sodium ion battery; welding and sealing, namely welding the conductive lugs of the core body and the cover plate, and then placing the conductive lugs and the cover plate into the shell for sealing and welding; baking and injecting liquid, namely vacuum baking the battery cells filled in the shell, and injecting liquid through the liquid injection holes after removing water; aging and forming, placing the battery cell after liquid injection in an environment at normal temperature or high temperature for a specified time to enable electrolyte to fully infiltrate into the pole piece, and then carrying out charge-discharge formation on the battery according to a specified formation system; and sealing, namely sealing the formed battery to form a sodium ion battery finished product. The sodium ion battery manufactured by the process has higher volume energy density, and meanwhile, the weight energy density is greatly improved, and the sodium ion battery has relatively good cycle life.
Optionally, the application further provides an electric device, and the electric device comprises a battery.
In one embodiment, the battery includes a lithium secondary battery or a sodium secondary battery; and/or the shell is made of aluminum, steel and plastic; and/or the battery comprises a hard-shell battery; and/or the shape of the battery includes square or cylindrical.
It is understood that the battery includes a battery cell, a battery module, and a battery pack.
It is understood that the battery includes, but is not limited to, a lithium secondary battery or a sodium secondary battery.
The material of the shell includes, but is not limited to, aluminum, steel, and plastic.
Batteries include, but are not limited to, hard-shell batteries.
The shape of the battery includes, but is not limited to, square or cylindrical.
It is understood that when the battery is a lithium ion battery, the positive electrode may be lithium cobaltate, ternary material, lithium manganate, lithium iron phosphate, lithium iron manganese phosphate or a mixture thereof, and the negative electrode may be artificial graphite, natural graphite, silicon-doped porous carbon, silicon oxide, stannous oxide, black scale or a mixture thereof.
When the battery is a sodium ion battery, the positive electrode may be a layered oxide, a polyanionic compound, and the negative electrode may be hard carbon, soft carbon, phosphorus doped porous carbon, or a mixture thereof.
The power utilization device comprises at least one of a secondary battery, a battery module or a battery pack provided by the application. The secondary battery, the battery module, or the battery pack may be used as a power source of the electric device, and may also be used as an energy storage unit of the electric device. The power utilization device may include, but is not limited to, mobile devices (e.g., cell phones, notebook computers, etc.), electric vehicles (e.g., electric only vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles, electric bicycles, electric scooters, electric golf carts, electric trucks, etc.), electric trains, ships and satellites, energy storage systems, and the like.
As the power consumption device, a battery cell, a battery module, or a battery pack may be selected according to the use requirements thereof.
For example, the electric device may be a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, or the like. To meet the high power and high energy density requirements of the power device for the battery cells, a battery pack or battery module may be employed.
As another example, the device may be a cell phone, tablet computer, notebook computer, or the like. The device is generally required to be light and thin, and a battery cell can be used as a power supply.
Comparative example 1
Taking a soft pack sodium ion battery as an example:
o3 phase layered oxide (NaNi 0.33 Fe 0.33 n 0.33 O 2 ) Conductive carbon black, PVDF, NMP according to 95:2.5:2.5:66, the positive electrode slurry was prepared according to the procedure described above, followed by 160mg/cm 2 Coating the surface density of the aluminum foil with the thickness of 16 microns, rolling, and punching into positive pole pieces with specified sizes;
hard carbon, conductive carbon black, CMC, SBR, water according to 93:2:1.5:3.5:140, preparing a negative electrode slurry according to the process, and then preparing a negative electrode slurry according to the ratio of 85mg/cm 2 Coating the surface density of the lithium ion battery on an aluminum foil with the thickness of 16 microns, and punching the lithium ion battery into a negative electrode plate of a high-energy-density battery with a specified size after rolling;
stacking the anode, the diaphragm, the cathode and the diaphragm at intervals by using a lamination method to form a core body, and then baking, liquid injection, aging, formation and sealing the core body according to the steps to form a battery with the capacity of about 2.2 Ah;
example 1
The preparation process of the positive electrode is the same as that of the preparation process of the positive electrode;
preparing negative electrode conductive slurry: conductive carbon black, CMC, SBR, water according to 2:1.5:3:140, preparing cathode conductive paste, and then coating a conductive layer with the thickness of 3 microns on a 16-micron aluminum foil;
preparing a negative electrode protective layer: fumed silica, PVDF, NMP according to 3:2:80, preparing a negative electrode protective adhesive layer, and then coating a protective layer with the thickness of 2 microns on the aluminum foil coated with the conductive coating;
then punching the substrate coated with the protective adhesive layer into a negative electrode plate of a high-energy-density battery with a specified size;
the soft package battery is manufactured according to the steps, and the positive and negative plates of the battery are the same in number as in comparative example 1;
example 2
The preparation process of the positive electrode is the same as that of the preparation process of the positive electrode;
preparing negative electrode conductive slurry: carbon nanotubes, CMC, SBR, water according to 2:1.5:3:140, preparing cathode conductive paste, and then coating a conductive coating with the thickness of 3 microns on a 16-micron aluminum foil;
preparing a negative electrode protective layer: fumed silica, PVDF, NMP according to 3:2:80, preparing a negative electrode protective adhesive layer, and then coating a protective adhesive layer with the thickness of 2 microns on the aluminum foil coated with the conductive coating;
then punching the substrate coated with the protective layer into a negative electrode plate of a high-energy-density battery with a specified size;
the soft package battery is manufactured according to the steps, and the positive and negative plates of the battery are the same in number as in comparative example 1;
example 3
The preparation process of the positive electrode is the same as that of the preparation process of the positive electrode;
preparing negative electrode conductive slurry: graphene, CMC, SBR, water according to 2:1.5:3:140, preparing cathode conductive paste, and then coating a conductive coating with the thickness of 3 microns on a 16-micron aluminum foil;
preparing a negative electrode protective layer: fumed silica, PVDF, NMP according to 3:2:80, preparing a negative electrode protective adhesive layer, and then coating a protective adhesive layer with the thickness of 2 microns on the aluminum foil coated with the conductive coating;
then punching the substrate coated with the protective adhesive layer into a negative electrode plate of a high-energy-density battery with a specified size;
the soft pack battery was fabricated in accordance with the foregoing procedure, and the same number of positive and negative electrode sheets as in comparative example 1 was used.
Performance testing
Volumetric specific energy test: charging the prepared battery to 4.0V at a constant current of 0.33C at 25 ℃, and then charging the battery to a constant voltage of 0.05C; after standing for 5min, the battery was discharged to 1.5V at a constant current of 0.33C to obtain discharge energy Q. Volumetric specific energy (Wh/L) of the battery=discharge energy Q/volume V of the battery.
Battery cycle performance test: charging to 4.0V at constant current of 1C under constant temperature environment of 25 ℃, then charging to 0.05C at constant voltage of 4.0V, and discharging to 1.5V at constant current of 1C to obtain first-week discharge specific capacity (C0); the charge and discharge were repeated until the 100 th week, and the specific discharge capacity after 100 weeks of the cycle was obtained and was denoted as Cn. Capacity retention = specific discharge capacity (Cn)/specific discharge capacity at first week (C0) after 100 weeks of cycling.
Table 1 list of examples
As can be seen from table 1, in the comparative examples and comparative examples, the battery performance was significantly improved by adopting the scheme of the conductive layer and the protective layer in the examples, which indicates that the negative electrode sheet of the high energy density battery in the present application is a non-negative active material layer, the thickness of the negative electrode sheet of the high energy density battery was reduced, the volumetric specific energy of the battery was increased, and the cycle performance of the battery was also improved.
The foregoing description of the preferred embodiments of the present invention should not be construed as limiting the scope of the invention, but rather as utilizing equivalent structural changes made in the description of the invention and the accompanying drawings, or as directly/indirectly employed in other related technical fields, are included in the scope of the invention.
Claims (10)
1. The negative electrode plate of the high-energy-density battery is characterized by comprising a current collector, a conductive layer arranged on at least one side of the current collector and a protective layer arranged on the surface of the conductive layer, wherein the conductive layer comprises a conductive agent, a thickening agent and a binder, the conductive agent comprises a carbon material, and the protective layer comprises an inorganic filler and an organic polymer.
2. The negative electrode tab of the high energy density battery of claim 1, wherein the conductive layer has a thickness of 1 μιη to 20 μιη;
and/or the particle diameter D50 of the conductive agent ranges from 5nm to 1 μm.
3. The negative electrode tab of a high energy density battery according to claim 1 or 2, wherein the mass ratio of the conductive agent, the thickener, and the binder is (2 parts to 20 parts): (0 to 3 parts): (2-8 parts).
4. The negative electrode tab of the high energy density battery of claim 3, wherein the conductive agent comprises at least one of carbon black, carbon nanotubes, graphene;
and/or the thickener comprises at least one of carboxymethyl cellulose, polyethylene oxide and polyacrylate;
and/or the binder comprises at least one of styrene-butadiene rubber, polyacrylate, polyethylene oxide and polyvinylidene fluoride.
5. The negative electrode sheet for a high energy density battery according to any one of claims 1 to 4, wherein the mass ratio of the inorganic filler to the organic polymer is (1 part to 10 parts): (1-10 parts).
6. The negative electrode tab of high energy density battery of claim 5 wherein the protective layer has a thickness of 1 μm to 20 μm ；
And/or the current collector comprises aluminum foil, copper foil, stainless steel foil, nickel foil;
and/or the particle diameter D50 of the inorganic filler ranges from 1nm to 1 μm.
7. The negative electrode for a high energy density battery of claim 6, wherein the inorganic filler comprises at least one of fumed silica, nano aluminum oxide, boehmite;
and/or the organic polymer comprises at least one of polyvinylidene fluoride, polymethyl methacrylate, polyimide and polyethylene oxide.
8. A method of producing the negative electrode sheet of a high energy density battery according to any one of claims 1 to 7, comprising:
preparing conductive agent slurry and protective layer slurry, and coating the conductive agent slurry and the protective layer slurry on at least one side of a current collector in a double-layer manner to obtain a negative electrode plate of the high-energy-density battery;
in the step of preparing the conductive agent paste and the protective layer paste, the steps of:
preparing a conductive agent, a thickener, a binder and a solvent, wherein the conductive agent, the thickener, the binder and the solvent are prepared according to the mass part ratio of (2-20): (0 to 3 parts): (2-8 parts): (80-180 parts) dissolving the thickener into a solvent, stirring, adding the conductive agent, dispersing, adding the binder, and dispersing to obtain the conductive agent slurry;
preparing an inorganic filler, an organic polymer and an organic solvent, wherein the mass ratio of the inorganic filler to the organic polymer to the organic solvent is (1-10): (1-10 parts): and (40-100 parts) dissolving the organic polymer into the organic solvent to form a mixed solution, adding the inorganic filler into the mixed solution, and dispersing to obtain the protective layer slurry.
9. A battery comprising an electrolyte, a positive electrode sheet and a negative electrode sheet of the high energy density battery of any one of claims 1 to 7;
or the battery comprises electrolyte and the negative electrode plate of the high-energy-density battery obtained by the preparation method of the negative electrode plate of the high-energy-density battery as claimed in claim 8;
the electrolyte is applied to a lithium ion battery and comprises lithium hexafluorophosphate lithium salt and one or more of dimethyl carbonate, ethylene carbonate, ethylmethyl carbonate, diethyl carbonate and propylene carbonate;
the electrolyte is applied to sodium ion batteries and comprises sodium hexafluorophosphate sodium salt and one or more of dimethyl carbonate, ethylene carbonate, methyl ethyl carbonate, diethyl carbonate and propylene carbonate;
the positive electrode plate is applied to a sodium ion battery and comprises at least one of sodium-containing layered oxide and polyanion sodium salt;
the positive pole piece is applied to a lithium ion battery and comprises at least one of lithium cobaltate, lithium ternary material, lithium manganate, lithium iron phosphate and lithium manganese iron phosphate;
the battery outer package comprises an aluminum-plastic composite film, a steel shell, an aluminum shell and a plastic shell;
the shape of the battery includes square and cylindrical.
10. An electrical device comprising the battery of claim 9.
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