WO2022205109A1 - 电化学装置和电子装置 - Google Patents
电化学装置和电子装置 Download PDFInfo
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- WO2022205109A1 WO2022205109A1 PCT/CN2021/084499 CN2021084499W WO2022205109A1 WO 2022205109 A1 WO2022205109 A1 WO 2022205109A1 CN 2021084499 W CN2021084499 W CN 2021084499W WO 2022205109 A1 WO2022205109 A1 WO 2022205109A1
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- active material
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- electrochemical device
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- thickener
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Images
Classifications
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
Definitions
- the present application relates to the field of electrochemical energy storage, in particular to electrochemical devices and electronic devices.
- the active material layer of the negative electrode is easy to expand, especially when the negative electrode material is silicon material, the expansion is more obvious, resulting in a decrease in the bonding force between the active material layer and the current collector, which easily leads to deformation.
- the amount of binder is increased, the energy density will be reduced, and the kinetic performance will be deteriorated. The deterioration of the kinetic performance will lead to an increase in polarization during high-rate charging, which is likely to cause lithium precipitation, thereby affecting the safety of electrochemical devices. performance. If the amount of binder is reduced in order to reduce the risk of lithium precipitation, it will increase the risk of demolding of the pole piece. The current improvement scheme is not satisfactory, and further improvement is expected.
- An embodiment of the present application provides an electrochemical device, including a negative electrode, and the negative electrode includes: a current collector and an active material layer on the current collector; the active material layer includes an inorganic thickener.
- the inorganic thickener includes: attapulgite, natural clay, aluminum silicate, magnesium aluminum silicate, lithium magnesium silicate, bentonite, diatomaceous earth, fumed silica, sodium bentonite, or silicon at least one of the gels.
- the inorganic thickener is a lamellar structure.
- the lamellar-structured particles have anions on their layers and the lamellar-structured particles have cations on their end faces.
- the cations include at least one of lithium ions, magnesium ions, or sodium ions.
- the mass percentage content of the inorganic thickener in the active material layer is 0.1% to 0.5%; the specific surface area of the inorganic thickener is 0.4m 2 /g to 100m 2 /g; the pH of the 1 wt % aqueous solution of the inorganic thickener is 7 to 10; the viscosity of the 1 wt % aqueous solution of the inorganic thickener is 100 mPa.s to 3000 mPa.s.
- the active material layer further comprises: an organic thickener; the organic thickener includes: carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose or At least one of lithium carboxymethyl cellulose.
- the mass percentage content of the organic thickener in the active material layer is 0.3% to 1.5%.
- the active material layer further includes: a binder; the mass percentage of the binder in the active material layer is 0.8% to 5%; the binder includes: styrene-butadiene rubber, fluorinated rubber, polystyrene At least one of acrylonitrile, polyacrylic acid, polyacrylate, polyvinyl alcohol, polytetrafluoroethylene or polyolefin.
- the cohesion of the active material layer is 30 N/m to 40 N/m; and/or the adhesive force between the active material layer and the current collector is 15 N/m to 20 N/m.
- the active material layer includes: a negative electrode material; the negative electrode material includes: at least one of natural graphite, artificial graphite, soft carbon, hard carbon, silicon, silicon carbon or silicon-oxygen material.
- an electronic device including the electrochemical device of any one of the above.
- the electrochemical device proposed in some embodiments of the present application includes: a positive electrode, a negative electrode, and a separator between the positive electrode and the negative electrode: wherein the negative electrode includes: a current collector and an active material layer on the current collector; the active material layer contains Inorganic thickener.
- inorganic thickeners are used to achieve the effect of improving the adhesion and cohesion of the negative electrode, thereby reducing the amount of thickeners, improving the kinetic performance and increasing the energy density of the electrochemical device.
- FIG. 1 shows a schematic diagram of particles of lamellar structure in some embodiments of the present application.
- FIG. 2 shows a schematic diagram of a colloidal structure in a three-dimensional space formed by particles of a lamellar structure in some embodiments of the present application.
- Electrochemical devices such as lithium-ion batteries are widely used in various fields.
- silicon materials are used as negative electrode materials in some technologies, but the volume expansion of silicon materials during the lithium intercalation process is large, resulting in The adhesive force of the active material layer of the negative electrode is seriously reduced, and may lead to the overall deformation of the cell.
- the amount of binder is increased, the energy density will be reduced, and the dynamic performance of the cell will be deteriorated.
- the deterioration of the kinetic performance leads to the increase of polarization during high-rate charging, which is likely to cause lithium precipitation, which in turn affects the safety performance.
- Reducing the ratio of the binder or thickening agent will reduce the adhesion between the active material layer of the negative electrode and the current collector, and increase the risk of film stripping of the pole piece, thereby affecting the performance of the electrochemical device.
- An embodiment of the present application provides an electrochemical device, including: a negative electrode, the negative electrode includes: a current collector and an active material layer on the current collector; the active material layer contains an inorganic thickener.
- the electrochemical device in the present application may be a lithium ion battery, the current collector in the negative electrode may be made of copper foil, or other materials may be used, the active material layer of the negative electrode may contain negative electrode material, and the negative electrode material may include carbon. Materials, such as graphite, may also include silicon materials, such as silicon dioxide.
- the active material layer of the negative electrode contains an inorganic thickening agent, which may be added to the negative electrode slurry when preparing the negative electrode, and then coating the negative electrode slurry on the current collector to form an active material layer.
- the inorganic thickener itself or with other materials can form a network or cross-linked structure to thicken, which improves the stability of the slurry. By using the inorganic thickener, the stability and rheological properties of the negative electrode slurry are improved.
- the adhesive force and cohesion of the anode have been improved to a certain extent, and the cycle performance of the electrochemical device has been improved to a certain extent; the amount of thickener and binder can be reduced, the polarization can be reduced, and the high-rate charging time can be shortened; at the same time, the active material of the negative electrode
- the adhesion between the layer and the current collector is improved, preventing the negative electrode from being filmed, and improving the kinetic performance of the negative electrode, which is beneficial to improve the cycle performance.
- the inorganic thickener includes: attapulgite, natural clay, aluminum silicate, magnesium aluminum silicate, lithium magnesium silicate, bentonite, diatomaceous earth, fumed silica, sodium bentonite, or silicon
- any one of the above-mentioned inorganic thickeners can be used in this application, and a mixture of at least two of the above-mentioned inorganic thickeners can also be used.
- the inorganic thickener is a lamellar structure.
- the lamellar-structured particles have anions on their layers and the lamellar-structured particles have cations on their end faces.
- the cations include at least one of lithium ions, magnesium ions, or sodium ions.
- FIG. 1 schematically shows a schematic diagram of particles of a lamellar structure, wherein the plane perpendicular to the thickness direction of the lamellar structure is the level of the lamellar structure, and the thickness direction of the lamellar structure is the layer of the lamellar structure.
- the surface facing the outer peripheral side of the lamella structure is the end surface of the lamella structure.
- the direction of the end surface may be perpendicular to the thickness direction of the lamella structure.
- the layer of the lamellar structure condensed by the inorganic thickener is covered with exchangeable cations. When the inorganic thickener is mixed with water, the water and the cations are in contact with the surface of the particles of the layered structure, and the particles of the layered structure are adsorbed. Spread apart from each other, the particles of the lamellar structure expand rapidly until the particles of the lamellar structure separate from each other.
- the end faces of the particles with the lamellar structure are negatively charged and the layers are positively charged, the end faces of the separated particles are attracted to the layer of another particle, thereby rapidly forming a three-dimensional colloidal structure (see Figure 2), that is, the card palace
- the structure increases the viscosity of the system, and has a high degree of suspension, thickening, thixotropy, good compatibility and chemical stability.
- the layered particles are ideal thickening rheological agents for water systems.
- the mass percentage content of the inorganic thickener in the active material layer is 0.1% to 0.5%. In some embodiments, the mass percentage content of the inorganic thickener in the active material layer is too low, which may not achieve a significant improvement effect, and the mass percentage content of the inorganic thickener in the active material layer is too high, which may affect the energy density.
- the specific surface area of the inorganic thickening agent is 0.4 m 2 /g to 100 m 2 /g; in some embodiments, the specific surface area of the inorganic thickening agent is too small, which may result in poor improvement effect due to less active surface. Obviously, when the specific surface area of the inorganic thickener is too large, the viscosity may increase too much and the improvement effect will be weakened.
- the pH of the 1 wt % aqueous solution of the inorganic thickener is 7 to 10.
- the inorganic thickening agent is a water-soluble material, and the inorganic thickening agent and water are prepared into a solution with a solid content of 1 wt %, and the results obtained by testing the pH value.
- a 1 wt % aqueous solution of the inorganic thickener has a viscosity of 100 mPa.s to 3000 mPa.s.
- the active material layer further comprises: an organic thickener; the organic thickener includes: carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, sodium carboxymethyl cellulose or At least one of lithium carboxymethyl cellulose.
- the particles of the inorganic thickener are actually multi-layered lamellar structured particles separated by a single layer of water molecules (see FIGS. 1 and 2 ). The higher the degree of separation between the particles of each layered structure, the stronger the structure, the greater the viscosity and yield value (dynamic shear force), and the more obvious the thickening effect. Since most organic thickeners do not have a yield value, inorganic thickeners are used in combination with organic thickeners to improve viscosity, yield value and fluidity.
- the mass percentage content of the organic thickener in the active material layer is 0.3% to 1.5%. In some embodiments, when the mass percentage of the organic thickener is too low, the improvement effect of the organic thickener is not obvious. When the mass percentage of the organic thickener is too high, the active material of the negative electrode may be caused. The conductivity of the layer decreases, which is detrimental to the kinetic performance.
- the active material layer further includes: a binder; the mass percentage of the binder in the active material layer is 0.8% to 5%; the binder includes: styrene-butadiene rubber, fluorinated rubber, polystyrene At least one of acrylonitrile, polyacrylic acid, polyacrylate, polyvinyl alcohol, polytetrafluoroethylene or polyolefin.
- the cohesion of the active material layer is 30 N/m to 40 N/m.
- the cohesive force of the active material layer is tested in the following manner, taking the pole piece to be tested, cutting a sample with a width of 30mm and a length of 100mm to 160mm with a blade, and sticking the double-sided tape on the steel plate, the width of the tape is 20mm, and the length is 90mm. To 150mm, stick the sample of the pole piece on the double-sided tape, the test surface is facing down, insert a paper tape with a width of 80mm to 200mm that is equal to the width of the pole piece and longer than the length of the sample under the pole piece, and use crepe glue. fixed.
- the adhesive force between the active material layer and the current collector is 15 N/m to 20 N/m.
- the cohesive force of the active material layer is tested in the following manner, taking the pole piece to be tested, cutting a sample with a width of 30mm and a length of 100mm to 160mm with a blade, and sticking the double-sided tape on the steel plate, the width of the tape is 20mm, and the length is 90mm.
- To 150mm stick the sample of the pole piece on the double-sided tape, the test surface is facing down, insert a paper tape with a width of 80mm to 200mm that is equal to the width of the pole piece and longer than the length of the sample under the pole piece, and use crepe glue. fixed.
- test method for cohesion and the test method for adhesion differ in the tape used.
- the active material layer includes: a negative electrode material; the negative electrode material includes: at least one of natural graphite, artificial graphite, soft carbon, hard carbon, silicon, silicon carbon or silicon-oxygen material.
- the silicon oxide material may be silicon dioxide, for example.
- the positive electrode of the above electrochemical device includes a current collector and an active material layer provided on the positive electrode current collector, and the positive electrode active material layer contains a positive electrode material.
- the specific types of cathode materials are not specifically limited, and can be selected according to requirements.
- the positive electrode material includes a positive electrode material capable of absorbing and releasing lithium (Li).
- Examples of cathode materials capable of absorbing/releasing lithium (Li) may include lithium cobalt oxide, lithium nickel cobalt manganate, lithium nickel cobalt aluminate, lithium manganate, lithium iron manganese phosphate, lithium vanadium phosphate, lithium vanadyl phosphate, phosphoric acid Lithium iron, lithium titanate, and lithium-rich manganese-based materials.
- the chemical formula of lithium cobalt oxide can be as chemical formula 1:
- M1 represents selected from nickel (Ni), manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), Copper (Cu), Zinc (Zn), Molybdenum (Mo), Tin (Sn), Calcium (Ca), Strontium (Sr), Tungsten (W), Yttrium (Y), Lanthanum (La), Zirconium (Zr) and At least one of silicon (Si), the values of x, a, b and c are respectively in the following ranges: 0.8 ⁇ x ⁇ 1.2, 0.8 ⁇ a ⁇ 1, 0 ⁇ b ⁇ 0.2, -0.1 ⁇ c ⁇ 0.2.
- nickel cobalt lithium manganate or nickel cobalt aluminate can be as chemical formula 2:
- M2 represents selected from cobalt (Co), manganese (Mn), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), at least one of copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), tungsten (W), zirconium (Zr) and silicon (Si),
- the values of y, d, e and f are respectively in the following ranges: 0.8 ⁇ y ⁇ 1.2, 0.3 ⁇ d ⁇ 0.98, 0.02 ⁇ e ⁇ 0.7, -0.1 ⁇ f ⁇ 0.2.
- the chemical formula of lithium manganate can be as chemical formula 3:
- M3 represents selected from cobalt (Co), nickel (Ni), magnesium (Mg), aluminum (Al), boron (B), titanium (Ti), vanadium (V), chromium (Cr), iron (Fe), At least one of copper (Cu), zinc (Zn), molybdenum (Mo), tin (Sn), calcium (Ca), strontium (Sr), and tungsten (W), with z, g and h values in the following ranges, respectively Inside: 0.8 ⁇ z ⁇ 1.2, 0 ⁇ g ⁇ 1.0 and -0.2 ⁇ h ⁇ 0.2.
- a conductive agent may be added to the active material layer of the positive electrode and the active material layer of the negative electrode of the above electrochemical device, and the conductive agent may include at least one of conductive carbon black, graphite, graphene, carbon nanotubes, carbon fibers or carbon black.
- the release membrane includes at least one of polyethylene, polypropylene, polyvinylidene fluoride, polyethylene terephthalate, polyimide, or aramid.
- the polyethylene includes at least one selected from high density polyethylene, low density polyethylene or ultra-high molecular weight polyethylene. Especially polyethylene and polypropylene, they have a good effect on preventing short circuits and can improve the stability of the battery through the shutdown effect.
- the thickness of the isolation film is in the range of about 5 ⁇ m to 500 ⁇ m.
- the surface of the separator may further include a porous layer, the porous layer is disposed on at least one surface of the substrate of the separator, the porous layer includes inorganic particles and a binder, and the inorganic particles are selected from alumina (Al 2 O 3 ), silicon oxide (SiO 2 ), magnesium oxide (MgO), titanium oxide (TiO 2 ), hafnium dioxide (HfO 2 ), tin oxide (SnO 2 ), ceria (CeO 2 ), nickel oxide (NiO) ), zinc oxide (ZnO), calcium oxide (CaO), zirconium oxide (ZrO 2 ), yttrium oxide (Y 2 O 3 ), silicon carbide (SiC), boehmite, aluminum hydroxide, magnesium hydroxide, hydroxide At least one of calcium or barium sulfate.
- alumina Al 2 O 3
- silicon oxide SiO 2
- magnesium oxide MgO
- titanium oxide TiO 2
- hafnium dioxide
- the pores of the isolation membrane have diameters in the range of about 0.01 ⁇ m to 1 ⁇ m.
- the binder of the porous layer is selected from the group consisting of polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, polyamide, polyacrylonitrile, polyacrylate, polyacrylic acid, polyacrylate, sodium carboxymethyl cellulose, polyamide At least one of vinylpyrrolidone, polyvinyl ether, polymethyl methacrylate, polytetrafluoroethylene or polyhexafluoropropylene.
- the porous layer on the surface of the separator can improve the heat resistance, oxidation resistance and electrolyte wettability of the separator, and enhance the adhesion between the separator and the pole piece.
- the electrochemical device is a wound electrochemical device or a stacked electrochemical device.
- the electrochemical device includes a lithium-ion battery, although the present application is not so limited.
- the electrochemical device further includes: an electrolyte, the electrolyte includes a polynitrile compound; the polynitrile compound includes: 1,3,6-hexanetricarbonitrile, 1,2,6-hexanetricarbonitrile, 1,3,6-hexanetricarbonitrile At least one of 3,5-pentanetricarbonitrile, 1,2,3-tris(2-cyanooxy)propane, succinonitrile or adiponitrile; wherein, the mass ratio of positive electrode material to polynitrile compound is 1 : (0.001 to 0.005).
- the electrolyte further includes a lithium salt and a non-aqueous solvent.
- the lithium salt is selected from LiPF6, LiBF4 , LiAsF6, LiClO4 , LiB ( C6H5 ) 4 , LiCH3SO3 , LiCF3SO3 , LiN ( SO2CF3 ) 2 , LiC ( SO2CF3 ) 3 , LiSiF 6 , LiBOB or one or more of lithium difluoroborate.
- LiPF 6 is chosen as the lithium salt because it can give high ionic conductivity and improve cycle characteristics.
- the non-aqueous solvent may be a carbonate compound, a carboxylate compound, an ether compound, other organic solvents, or a combination thereof.
- the carbonate compound may be a chain carbonate compound, a cyclic carbonate compound, a fluorocarbonate compound, or a combination thereof.
- chain carbonate compounds are diethyl carbonate (DEC), dimethyl carbonate (DMC), dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropyl carbonate (EPC), methyl carbonate Ethyl esters (MEC) and combinations thereof.
- Examples of the cyclic carbonate compound are ethylene carbonate (EC), propylene carbonate (PC), butylene carbonate (BC), vinylethylene carbonate (VEC), or a combination thereof.
- Examples of the fluorocarbonate compound are fluoroethylene carbonate (FEC), 1,2-difluoroethylene carbonate, 1,1-difluoroethylene carbonate, 1,1,2-trifluoroethylene carbonate Fluoroethylene, 1,1,2,2-tetrafluoroethylene carbonate, 1-fluoro-2-methylethylene carbonate, 1-fluoro-1-methylethylene carbonate, 1,2-carbonate -Difluoro-1-methylethylene carbonate, 1,1,2-trifluoro-2-methylethylene carbonate, trifluoromethylethylene carbonate, or a combination thereof.
- carboxylate compounds are methyl acetate, ethyl acetate, n-propyl acetate, tert-butyl acetate, methyl propionate, ethyl propionate, propyl propionate, ⁇ -butyrolactone, decolactone, Valerolactone, mevalonolactone, caprolactone, methyl formate, or a combination thereof.
- ether compounds are dibutyl ether, tetraglyme, diglyme, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethoxy Ethane, 2-methyltetrahydrofuran, tetrahydrofuran, or a combination thereof.
- organic solvents examples include dimethyl sulfoxide, 1,2-dioxolane, sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, N-methyl-2-pyrrolidone, methyl amide, dimethylformamide, acetonitrile, trimethyl phosphate, triethyl phosphate, trioctyl phosphate, and phosphate esters or combinations thereof.
- electrochemical devices eg, lithium ion batteries
- electrochemical devices eg, lithium ion batteries
- Other methods commonly used in the art may be employed without departing from the disclosure of the present application.
- Embodiments of the present application also provide electronic devices including the above electrochemical devices.
- the electronic device in the embodiment of the present application is not particularly limited, and it may be used in any electronic device known in the prior art.
- electronic devices may include, but are not limited to, notebook computers, pen input computers, mobile computers, e-book players, portable telephones, portable fax machines, portable copiers, portable printers, headsets, VCRs, LCD TVs, portable cleaners, portable CD players, mini discs, transceivers, electronic notepads, calculators, memory cards, portable recorders, radios, backup power supplies, motors, automobiles, motorcycles, assisted bicycles, bicycles, Lighting equipment, toys, game consoles, clocks, power tools, flashlights, cameras and large batteries for household use, etc.
- Lithium cobaltate, acetylene black and polyvinylidene fluoride are uniformly mixed in a weight ratio of 95:3:2, then the mixture is dispersed in a solvent, stirred and evacuated to obtain a positive electrode slurry. Then, the positive electrode slurry is uniformly coated on the aluminum foil, wherein the thickness of the aluminum foil can be between 8 ⁇ m and 13 ⁇ m. piece).
- CMC-Li Lithium Carboxymethyl Cellulose
- the lithium magnesium silicate powder was added to deionized water, and the solid content of the glue solution was 1.5%, and the solution was stirred at a slow speed of 500 rpm for 1 hour, and stirred evenly to obtain a lithium magnesium silicate glue solution.
- styrene-butadiene rubber binder to slurry 1, stir at a slow speed of 500rpm for 0.5h, add deionized water to adjust the solid content of slurry 1 to 48%, and then rapidly stir at a speed of 2000rpm for 1.5h to obtain a slurry Material 2, wherein the mass ratio of carbon material, binder, CMC and lithium magnesium silicate is 97:1.5:1.2:0.3.
- the obtained slurry 2 was filtered through a 150-mesh sieve to obtain a slurry 3.
- the slurry 3 is coated on the surface of the copper foil with a thickness of 10 ⁇ m, and is coated at a coating speed of 2 m/min.
- a negative electrode also called a negative electrode pole piece
- a coating thickness of 100 ⁇ m is obtained.
- PE polyethylene
- the positive electrode, the separator and the negative electrode are stacked in sequence, so that the separator is placed between the positive electrode and the negative electrode to play a role of isolation, and the electrode assembly is obtained by winding.
- the electrode assembly is placed in the outer packaging aluminum-plastic film, and after removing moisture at 80 °C, the electrolyte is injected and packaged, and the lithium ion battery is obtained through the process of formation, degassing, and trimming.
- each other embodiment and embodiment 1 is only one or more of the types and proportions of negative electrode material, binder, organic thickener, inorganic thickener in the negative electrode are different, and the specific differences are shown in the table below.
- the battery was discharged to 3V by 0.2C constant current discharge, and then charged to 100% SOC (state of charge) at a specific rate. This is one charge-discharge cycle, and after 10 charge-discharge cycles, a specific rate Charge the battery to 100% SOC. After charging is complete, disassemble it to check the lithium precipitation on the interface. Repeat the test until the minimum rate of lithium evolution of the battery is obtained.
- Test method Dissolve the powder of inorganic thickener in water to prepare an aqueous solution of 1% by mass, stir for 10 minutes, keep the temperature of the aqueous solution at 20°C to 25°C, and use a calibrated pH meter to directly test the pH value of the aqueous solution , test three times and take the average value.
- the adsorption amount of the sample monolayer is obtained based on the Brownnauer-Etter-Taylor adsorption theory and its formula, and the specific surface area of the solid is calculated. .
- W mass of gas adsorbed by solid sample under relative pressure
- Table 1 shows the respective parameters and evaluation results of Examples 1 to 5 and Comparative Examples 1 to 2.
- the preparation parameters of Examples 1 to 5 and Comparative Examples 1 to 2 differ only in the parameters shown in Table 1, and the rest of the preparation parameters are the same.
- the active material ratio, thickener 1 ratio, and thickener 2 content in Table 1 are the mass percentages of the active material layer, and "/" means not included.
- the inorganic thickeners were used in Examples 1 to 5, and the organic thickeners were used in Comparative Examples 1 and 2. It can be seen from Table 1 that the bonding force and cohesion of the negative electrode in Example 1 are much higher than those in Comparative Example 1. and 2, and the lithium deposition rate of the lithium ion batteries in Examples 1 to 5 is also much higher than that of Comparative Example 1. It can be seen that the use of inorganic thickeners in the negative electrode can reduce the amount of CMC and improve the adhesion, cohesion and dynamic performance.
- Table 2 shows the respective parameters and evaluation results of Examples 6 to 17 and Comparative Examples 3 to 5.
- the preparation parameters of Examples 6 to 17 and Comparative Examples 3 to 5 differ only in the parameters shown in Table 2, and the rest of the preparation parameters are the same.
- the active material ratio, thickener 1 ratio, and thickener 2 content in Table 2 are the mass percentages of the active material layer, and "/" means not included.
- Example 6 and Example 15 It can be seen from Example 6 and Example 15 that CMC-Li or CMC-Na (sodium carboxymethyl cellulose) as the organic thickener can achieve better results, and CMC-Li is used as the organic thickener The kinetic performance is better than using CMC-Na as organic thickener.
- CMC-Li or CMC-Na sodium carboxymethyl cellulose
- Example 18 to 22 The respective parameters and evaluation results of Examples 18 to 22 are shown in Table 3.
- the preparation parameters of Examples 18 to 22 differ from the preparation parameters of Example 1 only in the parameters shown in Table 3, and the other preparation parameters are the same.
- the content in Table 3 is the mass percentage content of the active material layer.
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Abstract
本申请提供了一种电化学装置和电子装置,其中,电化学装置,包括负极,负极包括:集流体和位于集流体至少一个表面上的活性物质层;活性物质层包含无机增稠剂。本申请中采用无机增稠剂达到提升负极粘接力和内聚力的效果,从而可以降低增稠剂用量,改善动力学性能的效果。
Description
本申请涉及电化学储能领域,尤其涉及电化学装置和电子装置。
随着电化学装置(例如,锂离子电池)的发展和进步,对其倍率性能提出了越来越高的要求。在大倍率充电过程中,负极的活性物质层容易膨胀,特别是当负极材料为硅材料时膨胀更为明显,导致活性物质层与集流体之间的粘结力下降,进而容易导致变形。如果增加粘结剂的用量,将导致能量密度降低,并且会恶化动力学性能,动力学性能的恶化会导致大倍率充电过程中极化增大,容易造成析锂,进而影响电化学装置的安全性能。如果为了降低析锂的风险而降低粘结剂的用量,由会增加极片的脱模风险。目前的改进方案尚不令人满意,期待进一步的改进。
发明内容
本申请的实施例中提供了一种电化学装置,包括负极,负极包括:集流体和位于集流体上的活性物质层;活性物质层包含无机增稠剂。
在一些实施例中,无机增稠剂包括:凹凸棒土、天然粘土、硅酸铝、硅酸镁铝、硅酸锂镁、膨润土、硅藻土、气相法白炭黑、钠基膨润土或硅凝胶中的至少一种。
在一些实施例中,无机增稠剂为片层结构。一些实施例中,片层结构的颗粒的层面上具有阴离子,片层结构的颗粒的端面上具有阳离子。一些实施例中,阳离子包括:锂离子、镁离子或钠离子中的至少一种。
在一些实施例中,满足如下条件中的至少一条:无机增稠剂在活性物质层中的质量百分含量为0.1%至0.5%;无机增稠剂的比表面积为0.4m
2/g至100m
2/g;无机增稠剂的1wt%水溶液的pH值为7至10;无机增稠剂的1wt%水溶液的粘度为100mPa.s至3000mPa.s。
在一些实施例中,活性物质层还包含:有机增稠剂;有机增稠剂包括:羧甲基纤维素、羟乙基纤维素、羟丙基甲基纤维素、羧甲基纤维素钠或羧甲基纤维素锂中的至少一种。
在一些实施例中,有机增稠剂在活性物质层的质量百分含量为0.3%至1.5%。在一些实施例中,活性物质层还包括:粘结剂;粘结剂在活性物质层中的质量百分含量为0.8%至5%;粘结剂包括:丁苯橡胶、氟化橡胶、聚丙烯腈、聚丙烯酸、聚丙烯酸酯、聚乙烯醇、聚四氟乙烯或聚烯烃中的至少一种。
在一些实施例中,活性物质层的内聚力为30N/m至40N/m;和/或,活性物质层与集流体之间的粘结力为15N/m至20N/m。
在一些实施例中,活性物质层包括:负极材料;负极材料包括:天然石墨、人造石墨、软碳、硬碳、硅、硅碳或硅氧材料中的至少一种。
在本申请的一些实施例中提出一种电子装置,包括上述任一项的电化学装置。
本申请的一些实施例中提出的电化学装置,包括:正极、负极和位于正极和负极之间的隔离膜:其中,负极包括:集流体和位于集流体上的活性物质层;活性物质层包含无机增稠剂。本申请中采用无机增稠剂达到提升负极粘接力和内聚力的效果,从而可以降低增稠剂用量,改善动力学性能并提升电化学装置能量密度的效果。
图1示出了本申请一些实施例中片层结构的颗粒的示意图。
图2示出了本申请一些实施例中片层结构的颗粒形成的三维空间的胶体结构的示意图。
下面的实施例可以使本领域技术人员更全面地理解本申请,但不以任何方式限制本申请。
电化学装置(例如锂离子电池)被广泛应用在各个领域,为了提高电化学装置的能量密度,一些技术中采用硅材料作为负极材料,但是硅材料 在嵌锂过程中的体积膨胀较大,导致负极的活性物质层的粘结力严重下降,并可能会导致电芯整体变形,如果增加粘结剂的用量会降低能量密度,并恶化电芯的动力学性能。动力学性能的恶化导致大倍率充电过程中的极化增大,容易造成析锂,进而影响安全性能。降低粘结剂或增稠剂的比例会导致负极的活性物质层与集流体之间的粘接力降低,极片脱膜风险增大,进而影响电化学装置的性能。
本申请的实施例中提供了一种电化学装置,包括:负极,负极包括:集流体和位于集流体上的活性物质层;活性物质层包含无机增稠剂。一些实施例中,本申请中的电化学装置可以是锂离子电池,负极中的集流体可以采用铜箔,也可以采用其他材料,负极的活性物质层中可以含有负极材料,负极材料可以包括碳材料,例如石墨,也可以包括硅材料,例如二氧化硅。负极的活性物质层中含有无机增稠剂,可以是在制备负极时,在负极浆料中加入无机增稠剂,然后将负极浆料涂覆在集流体上形成活性物质层,一些实施例,无机增稠剂本身或者与其他材料可形成网络或交联结构来增稠,提高了浆料的稳定性,通过使用无机增稠剂,负极浆料稳定性和流变性能得到提高,活性物质层的粘接力和内聚力有一定的提升,电化学装置的循环性能有一定的改善;可以降低增稠剂和粘结剂的量,减小极化,缩短大倍率充电时间;同时负极的活性物质层和集流体的粘接力提升,防止负极脱膜,提升负极的动力学性能,有利于改善循环性能。
在一些实施例中,无机增稠剂包括:凹凸棒土、天然粘土、硅酸铝、硅酸镁铝、硅酸锂镁、膨润土、硅藻土、气相法白炭黑、钠基膨润土或硅凝胶中的至少一种,本申请中可以采用上述中任一的无机增稠剂,也可以采用上述无机增稠剂中至少两个的混合物。
在一些实施例中,无机增稠剂为片层结构。一些实施例中,片层结构的颗粒的层面上具有阴离子,片层结构的颗粒的端面上具有阳离子。一些实施例中,阳离子包括:锂离子、镁离子或钠离子中的至少一种。一些实施例中,请参考图1,图1示意性的显示了片层结构的颗粒的示意图,其中垂直于片层结构的厚度方向的面为片层结构的层面,片层结构的厚度方向上的两个层面之间,朝向片层结构的外周侧的面为片层结构的端面,一些实施例中,端面的朝向可以与片层结构的厚度方向相垂直。无机增稠剂凝的片层结构的层 面布满了可交换的阳离子,当无机增稠剂与水混合时,水与阳离子接触被吸附到层状结构的颗粒的表面,将层状结构的颗粒彼此撑开,这时片层结构的颗粒迅速膨胀直至层状结构的颗粒彼此分离。由于片层结构的颗粒的端面带负电荷,层面带正电荷,分离后的颗粒的端面被吸引到另一颗粒的层面,从而迅速形成三维空间的胶体结构(请参看图2),即卡片宫结构,使体系的粘度增大,而具有高度的悬浮性、增稠性、触变性和良好的配伍性、化学稳定性,该层状结构的颗粒是理想的水体系增稠流变剂。
在一些实施例中,无机增稠剂在活性物质层中的质量百分含量为0.1%至0.5%。一些实施例中,无机增稠剂在活性物质层中的质量百分含量过低,可能无法起到明显的改善效果,无机增稠剂在活性物质层的质量百分含量过高,可能影响能量密度。
在一些实施例中,无机增稠剂的比表面积为0.4m
2/g至100m
2/g;一些实施例中,无机增稠剂的比表面积过小时,可能因为活性表面较少导致改善效果不明显,当无机增稠剂的比表面积过大时,可能会使得黏度增加过多导致改善效果减弱。
在一些实施例中,无机增稠剂的1wt%水溶液的pH值为7至10。一些实施例中,无机增稠剂为水溶性材料,将无机增稠剂和水制备成1wt%固含量的溶液测试pH值得到的结果。在一些实施例中,无机增稠剂的1wt%水溶液的粘度为100mPa.s至3000mPa.s。
在一些实施例中,活性物质层还包含:有机增稠剂;有机增稠剂包括:羧甲基纤维素、羟乙基纤维素、羟丙基甲基纤维素、羧甲基纤维素钠或羧甲基纤维素锂中的至少一种。在一些实施例中,在水体系中,无机增稠剂的颗粒实际上是被单层水分子隔开的多层的片层结构的颗粒(可参考图1和图2)。各个层状结构的颗粒彼此间的分隔的程度越高,其结构越坚固,粘度和屈服值(动切力)也越大,增稠效果也越明显。由于多数有机增稠剂不具屈服值,因而无机增稠剂与有机增稠剂复合使用,可以改善粘度、屈服值和流动性。
在一些实施例中,有机增稠剂在活性物质层的质量百分含量为0.3%至1.5%。一些实施例中,当有机增稠剂的质量百分含量过低时,有机增稠剂的改善效果不明显,当有机增稠剂的质量百分含量过高时,可能会导致负极的活性物质层的导电性下降,不利于动力学性能。
在一些实施例中,活性物质层还包括:粘结剂;粘结剂在活性物质层中的质量百分含量为0.8%至5%;粘结剂包括:丁苯橡胶、氟化橡胶、聚丙烯腈、聚丙烯酸、聚丙烯酸酯、聚乙烯醇、聚四氟乙烯或聚烯烃中的至少一种。
在一些实施例中,活性物质层的内聚力为30N/m至40N/m。一些实施例中,采用如下方式测试活性物质层的内聚力,取待测试极片,用刀片截取宽30mm,长度100mm至160mm的试样,将双面胶贴于钢板上,胶带宽度20mm,长度90mm至150mm,将极片的试样贴在双面胶上,测试面朝下,将宽度与极片等宽且长度大于试样长度的80mm至200mm的纸带插入极片下方,并且用皱纹胶固定。将钢板未贴极片的一端用下夹具固定。将纸带向上翻折,用上夹具固定,利用拉力机附带的手动控制器上的“上行”和“下行”按钮调整上夹具的位置。确认力传感器参数为“500N”,在试验项目一栏选择“粘结力测试”这一试验方案。图中曲线走平且位移大于10mm时,机器停止上升,界面上方“位移”参数自动归零。图中曲线走平且位移大于70mm时,机器停止上升,位移自动归零。读取图中曲线走平部分的平均值并记录。松开夹具,卸下试样。
活性物质层与集流体之间的粘结力为15N/m至20N/m。一些实施例中,采用如下方式测试活性物质层的内聚力,取待测试极片,用刀片截取宽30mm,长度100mm至160mm的试样,将双面胶贴于钢板上,胶带宽度20mm,长度90mm至150mm,将极片的试样贴在双面胶上,测试面朝下,将宽度与极片等宽且长度大于试样长度的80mm至200mm的纸带插入极片下方,并且用皱纹胶固定。将钢板未贴极片的一端用下夹具固定。将纸带向上翻折,用上夹具固定,利用拉力机附带的手动控制器上的“上行”和“下行”按钮调整上夹具的位置。确认力传感器参数为“500N”,在试验项目一栏选择“粘结力测试”这一试验方案。图中曲线走平且位移大于10mm时,机器停止上升,界面上方“位移”参数自动归零。图中曲线走平且位移大于70mm时,机器停止上升,位移自动归零。读取图中曲线走平部分的平均值并记录。松开夹具,卸下试样。一些实施例中,内聚力的测试方法和粘结力的测试方法的差异在于采用的胶带不同。
在一些实施例中,活性物质层包括:负极材料;负极材料包括:天然石墨、人造石墨、软碳、硬碳、硅、硅碳或硅氧材料中的至少一种。硅氧材料例如可以是二氧化硅。
上述电化学装置的正极包括集流体和设置在正极的集流体上的活性物质层,正极的活性物质层中含有正极材料。正极材料的具体种类均不受到具体的限制,可根据需求进行选择。在一些实施方案中,正极材料包括够吸收和释放锂(Li)的正极材料。能够吸收/释放锂(Li)的正极材料的例子可以包括钴酸锂、镍钴锰酸锂、镍钴铝酸锂、锰酸锂、磷酸锰铁锂、磷酸钒锂、磷酸钒氧锂、磷酸铁锂、钛酸锂和富锂锰基材料。
具体的,钴酸锂的化学式可以如化学式1:
Li
xCo
aM1
bO
2-c 化学式1
其中M1表示选自镍(Ni)、锰(Mn)、镁(Mg)、铝(Al)、硼(B)、钛(Ti)、钒(V)、铬(Cr)、铁(Fe)、铜(Cu)、锌(Zn)、钼(Mo)、锡(Sn)、钙(Ca)、锶(Sr)、钨(W)、钇(Y)、镧(La)、锆(Zr)和硅(Si)中的至少一种,x、a、b和c值分别在以下范围内:0.8≤x≤1.2、0.8≤a≤1、0≤b≤0.2、-0.1≤c≤0.2。
镍钴锰酸锂或镍钴铝酸锂的化学式可以如化学式2:
Li
yNi
dM2
eO
2-f 化学式2
其中M2表示选自钴(Co)、锰(Mn)、镁(Mg)、铝(Al)、硼(B)、钛(Ti)、钒(V)、铬(Cr)、铁(Fe)、铜(Cu)、锌(Zn)、钼(Mo)、锡(Sn)、钙(Ca)、锶(Sr)、钨(W)、锆(Zr)和硅(Si)中的至少一种,y、d、e和f值分别在以下范围内:0.8≤y≤1.2、0.3≤d≤0.98、0.02≤e≤0.7、-0.1≤f≤0.2。
锰酸锂的化学式可以如化学式3:
Li
zMn
2-gM3
gO
4-h 化学式3
其中M3表示选自钴(Co)、镍(Ni)、镁(Mg)、铝(Al)、硼(B)、钛(Ti)、钒(V)、铬(Cr)、铁(Fe)、铜(Cu)、锌(Zn)、钼(Mo)、锡(Sn)、钙(Ca)、锶(Sr)和钨(W)中的至少一种,z、g和h值分别在以下范围内:0.8≤z≤1.2、0≤g<1.0和-0.2≤h≤0.2。
上述电化学装置的正极的活性物质层和负极的活性物质层中可以加有导电剂,导电剂可以包括导电炭黑、石墨、石墨烯、碳纳米管、碳纤维或炭黑中的至少一种。
在一些实施例中,隔离膜包括聚乙烯、聚丙烯、聚偏氟乙烯、聚对苯二甲酸乙二醇酯、聚酰亚胺或芳纶中的至少一种。例如,聚乙烯包括选自高密度聚乙烯、低密度聚乙烯或超高分子量聚乙烯中的至少一种。尤其是聚乙烯和聚丙烯,它们对防止短路具有良好的作用,并可以通过关断效应改善电池的稳定性。在一些实施例中,隔离膜的厚度在约5μm至500μm的范围内。
在一些实施例中,隔离膜表面还可以包括多孔层,多孔层设置在隔离膜的基材的至少一个表面上,多孔层包括无机颗粒和粘接剂,无机颗粒选自氧化铝(Al
2O
3)、氧化硅(SiO
2)、氧化镁(MgO)、氧化钛(TiO
2)、二氧化铪(HfO
2)、氧化锡(SnO
2)、二氧化铈(CeO
2)、氧化镍(NiO)、氧化锌(ZnO)、氧化钙(CaO)、氧化锆(ZrO
2)、氧化钇(Y
2O
3)、碳化硅(SiC)、勃姆石、氢氧化铝、氢氧化镁、氢氧化钙或硫酸钡中的至少一种。在一些实施例中,隔离膜的孔具有在约0.01μm至1μm的范围的直径。多孔层的粘接剂选自聚偏氟乙烯、偏氟乙烯-六氟丙烯的共聚物、聚酰胺、聚丙烯腈、聚丙烯酸酯、聚丙烯酸、聚丙烯酸盐、羧甲基纤维素钠、聚乙烯呲咯烷酮、聚乙烯醚、聚甲基丙烯酸甲酯、聚四氟乙烯或聚六氟丙烯中的至少一种。隔离膜表面的多孔层可以提升隔离膜的耐热性能、抗氧化性能和电解质浸润性能,增强隔离膜与极片之间的粘接性。
在本申请的一些实施例中,电化学装置为卷绕式电化学装置或堆叠式电化学装置。在一些实施例中,电化学装置包括锂离子电池,但是本申请不限于此。
在一些实施例中,电化学装置还包括:电解液,电解液包括有多腈化合物;多腈化合物包括:1,3,6-己三甲腈、1,2,6-己三甲腈、1,3,5-戊三甲腈、1,2,3-三(2-氰氧基)丙烷、丁二腈或己二腈中的至少一种;其中,正极材料与多腈化合物的质量比为1:(0.001至0.005)。
在一些实施例中,电解液中还包括锂盐和非水溶剂。锂盐选自LiPF
6、LiBF
4、LiAsF
6、LiClO
4、LiB(C
6H
5)
4、LiCH
3SO
3、LiCF
3SO
3、LiN(SO
2CF
3)
2、 LiC(SO
2CF
3)
3、LiSiF
6、LiBOB或者二氟硼酸锂中的一种或多种。例如,锂盐选用LiPF
6,因为它可以给出高的离子导电率并改善循环特性。
非水溶剂可为碳酸酯化合物、羧酸酯化合物、醚化合物、其它有机溶剂或它们的组合。碳酸酯化合物可为链状碳酸酯化合物、环状碳酸酯化合物、氟代碳酸酯化合物或其组合。链状碳酸酯化合物的实例为碳酸二乙酯(DEC)、碳酸二甲酯(DMC)、碳酸二丙酯(DPC)、碳酸甲丙酯(MPC)、碳酸乙丙酯(EPC)、碳酸甲乙酯(MEC)及其组合。所述环状碳酸酯化合物的实例为碳酸亚乙酯(EC)、碳酸亚丙酯(PC)、碳酸亚丁酯(BC)、碳酸乙烯基亚乙酯(VEC)或者其组合。所述氟代碳酸酯化合物的实例为碳酸氟代亚乙酯(FEC)、碳酸1,2-二氟亚乙酯、碳酸1,1-二氟亚乙酯、碳酸1,1,2-三氟亚乙酯、碳酸1,1,2,2-四氟亚乙酯、碳酸1-氟-2-甲基亚乙酯、碳酸1-氟-1-甲基亚乙酯、碳酸1,2-二氟-1-甲基亚乙酯、碳酸1,1,2-三氟-2-甲基亚乙酯、碳酸三氟甲基亚乙酯或者其组合。
羧酸酯化合物的实例为乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸叔丁酯、丙酸甲酯、丙酸乙酯、丙酸丙酯、γ-丁内酯、癸内酯、戊内酯、甲瓦龙酸内酯、己内酯、甲酸甲酯或者其组合。
醚化合物的实例为二丁醚、四甘醇二甲醚、二甘醇二甲醚、1,2-二甲氧基乙烷、1,2-二乙氧基乙烷、乙氧基甲氧基乙烷、2-甲基四氢呋喃、四氢呋喃或者其组合。
其它有机溶剂的实例为二甲亚砜、1,2-二氧戊环、环丁砜、甲基环丁砜、1,3-二甲基-2-咪唑烷酮、N-甲基-2-吡咯烷酮、甲酰胺、二甲基甲酰胺、乙腈、磷酸三甲酯、磷酸三乙酯、磷酸三辛酯、和磷酸酯或者其组合。
本领域的技术人员将理解,以上描述的电化学装置(例如,锂离子电池)的制备方法仅是实施例。在不背离本申请公开的内容的基础上,可以采用本领域常用的其他方法。
本申请的实施例还提供了包括上述电化学装置的电子装置。本申请实施例的电子装置没有特别限定,其可以是用于现有技术中已知的任何电子装置。在一些实施例中,电子装置可以包括,但不限于,笔记本电脑、笔输入型计算机、移动电脑、电子书播放器、便携式电话、便携式传真机、 便携式复印机、便携式打印机、头戴式立体声耳机、录像机、液晶电视、手提式清洁器、便携CD机、迷你光盘、收发机、电子记事本、计算器、存储卡、便携式录音机、收音机、备用电源、电机、汽车、摩托车、助力自行车、自行车、照明器具、玩具、游戏机、钟表、电动工具、闪光灯、照相机和家庭用大型蓄电池等。
下面列举了一些具体实施例和对比例以更好地对本申请进行说明,其中,采用锂离子电池作为示例。
实施例1
正极制备:
将钴酸锂、乙炔黑和聚偏二氟乙烯按照重量比95:3:2混合均匀,然后将混合物分散在溶剂中经过搅拌、抽真空后获得正极浆料。然后通将正极浆料均匀涂覆在铝箔上,其中铝箔的厚度可以在8μm至13μm之间,烘干后辊压机进行压实,并经过分条,裁片,获得正极(也称正极极片)。
负极制备:
将CMC-Li(羧甲基纤维素锂)粉末加入到去离子水中,调配到胶液的固含量为1.5%,以500rpm的速度慢速搅拌5h,搅拌均匀得到CMC胶液。将硅酸锂镁粉末加入到去离子水中,调配到胶液的固含量为1.5%,以500rpm的速度慢速搅拌1h,搅拌均匀得到硅酸锂镁胶液。向获得的硅酸锂镁胶液中加入CMC胶液,获得增稠剂胶液;向获得的增稠剂胶液中加入人造石墨,以30rpm的速度慢速搅拌30min后,加入去离子水调整浆料的固含量至63%,再30rpm的速度捏合1.5h,获得浆料1。向浆料1中加入丁苯橡胶粘结剂,以500rpm的速度慢速搅拌0.5h,加入去离子水调整浆料1固含量至48%,然后再以2000rpm的速度快速搅拌1.5h,得到浆料2,其中碳材料、粘接剂、CMC和硅酸锂镁质量比为97:1.5:1.2:0.3。将获得的所述浆料2通过150目筛进行过滤获得浆料3。将所述浆料3涂布在10μm厚度的铜箔表面,以2m/min涂布速度进行涂布,涂布时,同时放到烤箱里用风机进行鼓风,实现加热烘干,风机速度为30m/s,烘箱温度为100℃,加热烘干后的得到涂层厚为100μm的负极(也成负极极片)。
隔离膜的制备:
使用多孔聚乙烯(PE)薄膜作为隔离膜;
锂离子电池的制备:
将正极、隔离膜、负极按顺序依次叠好,使隔离膜处于正极和负极中间起到隔离的作用,并卷绕得到电极组件。将电极组件置于外包装铝塑膜中,在80℃下脱去水分后,注入电解液并封装,经过化成,脱气,切边等工艺流程得到锂离子电池。
其他各个实施例与实施例1区别仅在于负极中负极材料、粘结剂、有机增稠剂、无机增稠剂的种类和比例中的一个或多个不同,具体差异见下方表.
下面描述本申请的各个参数的测试方法。
粘结力测试:
取待测试极片,用刀片截取宽30mm,长度100mm至160mm的试样,将双面胶贴于钢板上,胶带宽度20mm,长度90mm至150mm,将极片的试样贴在双面胶上,测试面朝下,将宽度与极片等宽且长度大于试样长度的80mm至200mm的纸带插入极片下方,并且用皱纹胶固定。将钢板未贴极片的一端用下夹具固定。将纸带向上翻折,用上夹具固定,利用拉力机附带的手动控制器上的“上行”和“下行”按钮调整上夹具的位置。确认力传感器参数为“500N”,在试验项目一栏选择“粘结力测试”这一试验方案。图中曲线走平且位移大于10mm时,机器停止上升,界面上方“位移”参数自动归零。图中曲线走平且位移大于70mm时,机器停止上升,位移自动归零。读取图中曲线走平部分的平均值并记录。松开夹具,卸下试样。
内聚力测试:
取待测试极片,用刀片截取宽30mm,长度100mm至160mm的试样,将双面胶贴于钢板上,胶带宽度20mm,长度90mm至150mm,将极片的试样贴在双面胶上,测试面朝下,将宽度与极片等宽且长度大于试样长度的80mm至200mm的纸带插入极片下方,并且用皱纹胶固定。将钢板未贴极片的一端用下夹具固定。将纸带向上翻折,用上夹具固定,利用拉力机附带的手动控制器上的“上行”和“下行”按钮调整上夹具的位置。确认力传感器参数为“500N”,在试验项目一栏选择“粘结力测试”这一试验方案。图中曲线走平且位移大于10mm时,机器停止上升,界面上方“位移”参数自动归零。图中曲线走平且位移大于70mm时,机器停止上升,位移自动归零。 读取图中曲线走平部分的平均值并记录。松开夹具,卸下试样。内聚力的测试方法和粘结力的测试方法的差异在于采用的胶带不同。
析锂倍率测试方法:
在25℃下,采用0.2C恒流放电将电池放电至3V,然后以特定倍率充电至100%SOC(荷电状态),此为1次充放电循环,进行10次充放电循环后采用特定倍率将电池充电至100%SOC,充电完成后,拆解查看界面析锂情况。重复测试直到测试得到电池析锂的最小倍率。
无机增稠剂的pH测试方法:
依据《GB/T 9724-2007化学试剂pH值测定通则》测试pH值,采用仪器:雷磁PHS-3C型pH计,电极:E-201F pH复合电极;
测试方法:将无机增稠剂的粉体溶解于水中制备成1%质量百分含量的水溶液,搅拌10min,水溶液温度保持在20℃至25℃,采用校正好的pH计直接测试水溶液的pH值,测试三次,取平均值。
比表面积(BET)测试方法:
在恒温低温下,测定不同相对压力时的气体在固体表面的吸附量后,基于布朗诺尔-埃特-泰勒吸附理论及其公式求得试样单分子层吸附量,从而计算出固体的比表面积。
其中:W—相对压力下固体样品所吸附的气体的质量
Wm---铺满一单分子层的气体饱和吸附量
斜率:(c-1)/(WmC),截距:1/WmC,总比表面积:(Wm*N*Acs/M)
比表面积:S=St/m,其中m为样品质量,Acs:每个N
2分子的所占据的平均面积16.2A
2。
称取1.5g至3.5g粉末样品装入TriStar II 3020的测试测试样品管中,200℃脱气120min后进行测试。。
表1示出了实施例1至5和对比例1至2的各个参数和评估结果。实施例1至5和对比例1至2的制备参数的区别仅在于表1所示的参数,其余制备参数均相同。
表1
注:表1中的活性材料比例、增稠剂1比例、增稠剂2含量为占活性物质层的质量百分含量,“/”表示不含。
实施例1至5中采用了无机增稠剂,对比例1和2中采用了有机增稠剂,从表1中可以看出实施例1中负极的粘结力和内聚力远高于对比例1和2,且实施例1至5中锂离子电池的析锂倍率也远高于对比例1,由此可见,在负极中使用无机增稠剂能够降低CMC的用量,提高粘结力、内聚力和动力学性能。
对比实施例1至5可以看出,采用不同类型的无机增稠剂均能够改善负极的粘结力、内聚力和ALP,其中,当无机增稠剂为硅酸锂镁时性能最好。
表2示出了实施例6至17和对比例3至5的各个参数和评估结果。实施例6至17和对比例3至5的制备参数的区别仅在于表2所示的参数,其余制备参数均相同。
表2
注:表2中的活性材料比例、增稠剂1比例、增稠剂2含量为占活性物质层的质量百分含量,“/”表示不含。
从实施例6至8可以看出,当硅酸锂镁在负极的活性物质层中的质量百分含量为0.1%至0.5%范围内时,均具有较好的改善效果,其中当硅酸锂镁在负极的活性物质层中的质量百分含量为0.3%时效果最佳。
从实施例6、9至12可以看出,在负极材料为人造石墨、天然石墨、人造石墨和硅碳的混合物、或者人造石墨和硅氧的混合物时,均能够实现较好的效果,不同负极材料表面性能不同个,因此动力学性能存在差异。
从实施例6、13至14可以看出,粘结剂为丁苯橡胶、聚丙烯腈、聚丙烯酸时均能实现较好的效果,可以看出,采用溶液型高分子类型的粘结剂能够实现较强的粘结力。
从实施例6和实施例15可以看出,有机增稠剂为CMC-Li或CMC-Na(羧甲基纤维素钠)均能实现较好的效果,其中采用CMC-Li作为有机增稠剂时动力学性能优于采用CMC-Na作为有机增稠剂。
从实施例6、16至17可以看出,有机增稠剂在负极的活性物质层的质量百分含量为0.8%至1.2%时均能实现较好的效果。
实施例18至22的各个参数和评估结果如表3所示。实施例18至22的制备参数与实施例1的制备参数的区别仅在于表3所示的参数,其余制备参数均相同。
表3
注:表3中的含量为占活性物质层的质量百分含量。
对比实施例18至22可以看到,随着无机增稠剂的质量百分含量的增加,粘结力和析锂倍率均先增加后降低,在无机增稠的质量百分含量为0.1%至1%范围内时,改善效果较好。
从表3中可以看出,无机增稠剂的水溶液为中性至弱碱性,无机增稠剂的比表面积在0.4m
2/g至0.8m
2/g之间时,均有较好的改善效果。
以上描述仅为本申请的较佳实施例以及对所运用技术原理的说明。本领域技术人员应当理解,本申请中所涉及的公开范围,并不限于上述技术特征的特定组合而成的技术方案,同时也应涵盖由上述技术特征或其等同特征进行任意组合而形成的其它技术方案。例如上述特征与本申请中公开的具有类似功能的技术特征进行互相替换而形成的技术方案。
Claims (12)
- 一种电化学装置,其特征在于,包括负极,其中,所述负极包括:集流体和位于所述集流体至少一个表面上的活性物质层;所述活性物质层包含无机增稠剂。
- 根据权利要求1所述的电化学装置,其特征在于,所述无机增稠剂包括:凹凸棒土、天然粘土、硅酸铝、硅酸镁铝、硅酸锂镁、膨润土、硅藻土、气相法白炭黑、钠基膨润土或硅凝胶中的至少一种。
- 根据权利要求1所述的电化学装置,其特征在于,所述无机增稠剂为片层结构。
- 根据权利要求3所述的电化学装置,其特征在于,所述片层结构的颗粒的层面上具有阴离子,所述片层结构的颗粒的端面上具有阳离子。
- 根据权利要求4所述的电化学装置,其特征在于,所述阳离子包括锂离子、镁离子或钠离子中的至少一种。
- 根据权利要求1所述的电化学装置,其特征在于,满足如下条件中的至少一条:所述无机增稠剂在所述活性物质层中的质量百分含量为0.1%至0.5%;所述无机增稠剂的比表面积为0.4m 2/g至100m 2/g;所述无机增稠剂的1wt%水溶液的pH值为7至10;所述无机增稠剂的1wt%的水溶液的粘度为100mPa.s至3000mPa.s。
- 根据权利要求1所述的电化学装置,其特征在于,所述活性物质层还包含:有机增稠剂;所述有机增稠剂包括:羧甲基纤维素、羟乙基纤维素、羟丙基甲基纤维素、羧甲基纤维素钠或羧甲基纤维素锂中的至少一种。
- 根据权利要求1所述的电化学装置,其特征在于,所述有机增稠剂在所述活性物质层的质量百分含量为0.3%至1.5%。
- 根据权利要求1所述的电化学装置,其特征在于,所述活性物质层还包括:粘结剂;所述粘结剂在活性物质层中的质量百分含量为0.8%至5%;所述粘结剂包括:丁苯橡胶、氟化橡胶、聚丙烯腈、聚丙烯酸、聚丙烯酸酯、聚乙烯醇、聚四氟乙烯或聚烯烃中的至少一种。
- 根据权利要求1所述的电化学装置,其特征在于,所述活性物质层的内聚力为30N/m至40N/m;和/或,所述活性物质层与集流体之间的粘结力为15N/m至20N/m。
- 根据权利要求1所述的电化学装置,其特征在于,所述活性物质层包括:负极材料;所述负极材料包括:天然石墨、人造石墨、软碳、硬碳、硅、硅碳或硅氧材料中的至少一种。
- 一种电子装置,包括根据权利要求1至11中任一项所述的电化学装置。
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