WO2021120858A1 - High-wetting long-cycle alumina ceramic slurry and preparation method therefor, and lithium battery diaphragm - Google Patents

High-wetting long-cycle alumina ceramic slurry and preparation method therefor, and lithium battery diaphragm Download PDF

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WO2021120858A1
WO2021120858A1 PCT/CN2020/123947 CN2020123947W WO2021120858A1 WO 2021120858 A1 WO2021120858 A1 WO 2021120858A1 CN 2020123947 W CN2020123947 W CN 2020123947W WO 2021120858 A1 WO2021120858 A1 WO 2021120858A1
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alumina
ceramic slurry
alumina ceramic
pore volume
dispersant
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PCT/CN2020/123947
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French (fr)
Chinese (zh)
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王成豪
贡晶晶
尚文滨
张立斌
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江苏厚生新能源科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/06—Coating with compositions not containing macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • 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 invention belongs to the technical field of lithium battery diaphragms, and specifically relates to a high-wetting long-cycle alumina ceramic slurry and a preparation method thereof, and a lithium battery diaphragm.
  • the purpose of the present invention is to provide an alumina ceramic slurry and a preparation method, and a lithium battery diaphragm.
  • the present invention provides an alumina ceramic slurry, which includes the following raw materials: solid alumina, dispersant, wetting agent, binder, thickener, defoamer, and pure water.
  • the solid alumina includes: high pore volume alumina and/or low pore diameter alumina; wherein
  • the pore volume distribution of the high pore volume alumina is 0.4-3.0 ml/g;
  • the pore size distribution of the low pore size alumina is 0.1-5nm.
  • the mass ratio of high pore volume alumina and low pore diameter alumina is 1:0.1-10.
  • the mass ratio of the solid alumina, dispersant, wetting agent, binder, thickener, defoamer, and pure water is 1:0.001-0.01:0.003-0.009:0.01-0.08:0.005. -0.015: 0-0.06: 1-2.5.
  • the dispersant includes one or more of silicates, alkali metal phosphates, organic dispersants, sodium salt dispersants, and ammonium salt dispersants; wherein the silicates include water glass;
  • the alkali metal phosphates include at least one of sodium tripolyphosphate, sodium hexametaphosphate, and sodium pyrophosphate;
  • the organic dispersant includes triethylhexyl phosphoric acid, sodium lauryl sulfate, and methylpentanol , Cellulose derivatives, polyacrylamide, Guer gum, fatty acid polyethylene glycol ester, one or more of them.
  • the wetting agent includes at least one of anionic surfactants, nonionic surfactants, and neutral surfactants.
  • the binder includes an aqueous binder.
  • the thickener includes sodium carboxymethacrylate.
  • the defoamer includes isopropanol.
  • the present invention also provides a method for preparing alumina ceramic slurry, which is to stir and mix solid alumina, dispersant, wetting agent, binder, thickener, defoamer, and pure water. Dispersed to form the alumina ceramic slurry.
  • the present invention also provides a lithium battery separator, which includes a PE film and an alumina ceramic slurry coated on the PE film.
  • the beneficial effect of the present invention is that the alumina ceramic slurry of the present invention and the preparation method thereof, the lithium battery diaphragm adopts solid alumina and other components to be mixed and dispersed to form alumina ceramic slurry for the preparation of lithium battery diaphragm, greatly reducing The wetting time of the separator is improved, and the production efficiency of the battery is improved.
  • Figure 1 is a comparison diagram of the cycle capacity of a doped alumina battery and a conventional alumina battery; the ordinate is the battery capacity holding rate, and the abscissa is the number of cycles;
  • Figure 2 is a comparison diagram of the wetting time of a doped alumina battery and a conventional alumina battery
  • Figure 3 is a comparison diagram of the cycle capacity of a high pore volume alumina battery and a conventional alumina battery; the ordinate is the battery capacity retention rate, and the abscissa is the number of cycles;
  • Figure 4 is a comparison diagram of the wetting time of a low pore size alumina battery and a conventional alumina battery.
  • high pore volume alumina and low pore diameter alumina on cycle capacity and diaphragm wetting time is as follows: high pore volume can increase the porosity of alumina and store more electrolyte, while low pore volume can increase the capillary effect and enhance alumina absorption The speed of the electrolyte improves the wetting efficiency.
  • the alumina ceramic slurry of Example 1 includes the following raw materials: solid alumina, dispersant, wetting agent, binder, thickener, defoamer, and pure water.
  • the solid content of the alumina ceramic slurry is 10-60%, preferably 30-40%.
  • the mass ratio of the solid alumina, dispersant, wetting agent, binder, thickener, defoamer, and pure water is 1:0.001-0.01:0.003-0.009:0.01-0.08. : 0.005-0.015: 0-0.06: 1-2.5.
  • the mass ratio of the solid alumina, dispersant, wetting agent, binder, thickener, defoamer, and pure water is 1:0.001-0.01:0.003-0.009:0.01-0.08 in order: 0.005-0.015: 0-0.06: 1-2.5.
  • the solid alumina includes: high pore volume alumina and/or low pore diameter alumina; the pore volume distribution of the high pore volume alumina is 0.4-3.0 ml/g; the pore volume distribution of the low pore volume alumina is 0.1 -5nm; and the mass ratio of alumina with high pore volume and alumina with low pore volume is 1:0.1-10.
  • the pore volume distribution of the high pore volume alumina is 0.5-1.5 ml/g, more preferably 1 ml/g; and the pore volume distribution of the low pore volume alumina is 0.1-1 nm, more preferably 0.6 nm.
  • the pore volume and pore size distribution range of this alumina can not only store more electrolyte and improve the wetting efficiency, but also facilitate industrial production.
  • the mass ratio of high pore volume alumina and low pore diameter alumina is 1:0.5-8, preferably 1:1-5, so that the liquid storage capacity and wetting capacity of the alumina ceramic slurry can be balanced.
  • the alumina ceramic slurry of Example 1 mixes solid alumina with low pore size alumina and/or high pore volume alumina, and mixes and disperses with other components to form alumina ceramic slurry, which can be enlarged by using low pore size alumina.
  • Capillary effect increases the rate at which alumina absorbs electrolyte and improves wetting efficiency; using high pore volume alumina can increase the porosity of alumina and store more electrolyte to increase the cycle life of lithium batteries, thereby ensuring alumina ceramic slurry
  • the liquid storage capacity and wetting capacity of the material are taken into account, which greatly reduces the wetting time of the separator and improves the production efficiency of the battery.
  • the dispersant includes, but is not limited to, one or more of silicates, alkali metal phosphates, organic dispersants, sodium salt dispersants, and ammonium salt dispersants; wherein the dispersants are silicates.
  • Types include but are not limited to water glass;
  • the alkali metal phosphates include but are not limited to at least one of sodium tripolyphosphate, sodium hexametaphosphate, and sodium pyrophosphate;
  • the organic dispersant includes, but is not limited to, triethyl One or more of hexyl phosphoric acid, sodium lauryl sulfate, methylpentanol, cellulose derivatives, polyacrylamide, Guer gum, and fatty acid polyethylene glycol esters.
  • the function of the dispersant is mainly to uniformly disperse the solid alumina in the solvent. There are some residual functional groups (such as -OH) during the production of solid alumina, which will cause side reactions with part of the dispersant and cause agglomeration.
  • the wetting agent includes but is not limited to at least one of anionic surfactants, nonionic surfactants, and neutral surfactants.
  • the main function of the wetting agent is to reduce the surface tension of the alumina ceramic slurry without affecting the circulation capacity and wetting time, so that the alumina ceramic slurry can be coated on the diaphragm.
  • the adhesive includes but is not limited to an aqueous adhesive, such as but not limited to an acrylic adhesive.
  • the main function of the binder is to bond the alumina ceramic slurry to the diaphragm without affecting the cycle capacity and wetting time, to prevent the alumina ceramic slurry from falling off, and to improve the stability of the diaphragm.
  • the thickener includes, but is not limited to, sodium carboxymethacrylate.
  • the role of the thickener is mainly to adjust the viscosity of the alumina ceramic slurry, to ensure the smoothness of the slurry and to avoid the slurry from settling too fast.
  • the thixotropic index of the thickener should be high, and the viscosity will become thin under high shearing force. . At the same time, it must be ensured that the circulation capacity and wetting time are not affected.
  • the defoamer includes but is not limited to isopropanol.
  • the main function of the defoamer is to reduce the number of bubbles in the alumina ceramic slurry to avoid reaction with other components in the slurry.
  • this Example 2 also provides a preparation method of alumina ceramic slurry, that is, solid alumina, dispersant, wetting agent, binder, thickener, defoamer, Pure water is stirred and mixed for dispersion to form the alumina ceramic slurry.
  • alumina ceramic slurry that is, solid alumina, dispersant, wetting agent, binder, thickener, defoamer, Pure water is stirred and mixed for dispersion to form the alumina ceramic slurry.
  • the dispersion method includes high-speed dispersion using a double planetary or sand mill.
  • this Embodiment 3 also provides a lithium battery separator, which includes a PE film and an alumina ceramic slurry coated on the PE film.
  • the PE film is 12 ⁇ m
  • the coating thickness of the alumina ceramic slurry is 2 ⁇ m
  • two layers are coated, that is, a doped alumina battery or a high-porosity alumina battery or a low-volume alumina battery with a specification of 12 ⁇ m+2 ⁇ m+2 ⁇ m.
  • Alumina cell with pore size is 12 ⁇ m
  • the coating thickness of the alumina ceramic slurry is 2 ⁇ m
  • two layers are coated, that is, a doped alumina battery or a high-porosity alumina battery or a low-volume alumina battery with a specification of 12 ⁇ m+2 ⁇ m+2 ⁇ m.
  • a high pore volume alumina with a pore volume of 1.0 ml/g and a low pore diameter alumina with a pore diameter of 1 nm are selected through specific detection equipment, and 50 kg of doped alumina ceramic slurry is configured.
  • a high pore volume alumina with a pore volume of 0.4 ml/g and a low pore diameter alumina with a pore volume of 0.1 nm are selected to configure the doped alumina ceramic slurry.
  • a high pore volume alumina with a pore volume of 3 ml/g and a low pore diameter alumina with a pore volume of 5 nm are selected to configure the doped alumina ceramic slurry.
  • a high pore volume alumina with a pore volume of 1.5 ml/g and a low pore diameter alumina with a pore volume of 3 nm are selected to configure the doped alumina ceramic slurry.
  • a conventional alumina with a pore volume of 0.3ml/g and a pore diameter of 8nm is selected, and 50kg of conventional alumina ceramic slurry is configured.
  • a PE film of 12 ⁇ m is used, and a conventional alumina ceramic slurry of 2 ⁇ m is coated to form a conventional alumina battery with a specification of 12 ⁇ m + 2 ⁇ m + 2 ⁇ m.
  • a PE film of 12 ⁇ m is used, and a conventional alumina ceramic slurry of 2 ⁇ m is coated to form a conventional alumina battery with a specification of 12 ⁇ m + 2 ⁇ m + 2 ⁇ m.
  • Example 10 the batteries prepared by coating the slurry in Examples 4-6 and Comparative Examples 1-3 were tested to detect the cycle capacity and wetting time of the separator. The results are shown in Table 1.
  • Figure 1 is a comparison diagram of the cycle capacity of a doped alumina battery and a conventional alumina battery.
  • Figure 2 is a comparison chart of the wetting time of a doped alumina battery and a conventional alumina battery.
  • Figure 3 is a comparison diagram of the cycle capacity of a high pore volume alumina battery and a conventional alumina battery.
  • Figure 4 is a comparison diagram of the wetting time of a low pore size alumina battery and a conventional alumina battery.
  • the wetting time of the low-pore alumina battery in this case is 10S, which is much lower than the 30S of the conventional alumina battery.
  • the main reason is that the use of low-pore alumina can increase the capillary effect, increase the rate at which the alumina absorbs the electrolyte, and improve the wetting efficiency.
  • the lithium battery separator is mixed with low-pore alumina and/or high-porosity alumina through solid alumina, and mixed and dispersed with other components to form Alumina ceramic slurry
  • high pore volume alumina can increase the porosity of alumina and store more electrolyte to increase the cycle life of lithium batteries
  • low pore alumina can increase the capillary effect and increase the rate at which alumina absorbs electrolyte
  • Improve the wetting efficiency greatly reduce the wetting time of the separator, thereby improving the production efficiency of the battery.
  • the battery's liquid storage capacity and wetting ability can also be taken into account. , To achieve the effect of high wetting and long circulation.

Abstract

A high-wetting long-cycle alumina ceramic slurry and a preparation method therefor. The alumina ceramic slurry comprises the following raw materials: solid alumina, a dispersant, a wetter, a binder, a thickener, a defoamer, and pure water. The solid alumina comprises: high pore volume alumina and/or low pore diameter alumina; wherein the pore volume distribution of the high pore volume alumina is 0.4-3.0 ml/g, and the pore diameter distribution of the low pore diameter alumina is 0.1-5 nm. A lithium battery diaphragm comprises a PE film and the alumina ceramic slurry coated on the PE film. The use of the solid alumina greatly reduces the wetting time of the diaphragm and improves the production efficiency of batteries.

Description

高润湿长循环的氧化铝陶瓷浆料及制备方法、锂电池隔膜High-wetting long-cycle alumina ceramic slurry and preparation method thereof, and lithium battery diaphragm 技术领域Technical field
本发明属于锂电池隔膜技术领域，具体涉及一种高润湿长循环的氧化铝陶瓷浆料及制备方法、锂电池隔膜。The invention belongs to the technical field of lithium battery diaphragms, and specifically relates to a high-wetting long-cycle alumina ceramic slurry and a preparation method thereof, and a lithium battery diaphragm.
背景技术Background technique
传统氧化铝的孔径较大，导致其毛细效应差，电解液进入困难，致使电解液润湿能力一般，因此传统氧化铝浆料涂覆隔膜限制了锂电池隔膜吸收电解液的速率，从而导致了锂电池注液之后陈化时间较长，隔膜润湿不够充分，导致电池界面出现黑斑、低容等不良。Traditional alumina has a large pore size, resulting in poor capillary effect and difficulty in entering the electrolyte, resulting in average wetting ability of the electrolyte. Therefore, the traditional alumina slurry coating diaphragm limits the rate at which the lithium battery diaphragm absorbs the electrolyte, which leads to Lithium batteries have a long aging time after liquid injection, and the separator is not sufficiently wetted, resulting in black spots and low capacity on the battery interface.
发明内容Summary of the invention
本发明的目的是提供一种氧化铝陶瓷浆料及制备方法、锂电池隔膜。The purpose of the present invention is to provide an alumina ceramic slurry and a preparation method, and a lithium battery diaphragm.
为了解决上述技术问题，本发明提供了一种氧化铝陶瓷浆料，包括以下原料：固态氧化铝、分散剂、润湿剂、粘结剂、增稠剂、消泡剂、纯水。In order to solve the above technical problems, the present invention provides an alumina ceramic slurry, which includes the following raw materials: solid alumina, dispersant, wetting agent, binder, thickener, defoamer, and pure water.
进一步，所述固态氧化铝包括：高孔容氧化铝和/或低孔径氧化铝；其中Further, the solid alumina includes: high pore volume alumina and/or low pore diameter alumina; wherein
所述高孔容氧化铝的孔容分布为0.4-3.0ml/g；The pore volume distribution of the high pore volume alumina is 0.4-3.0 ml/g;
所述低孔径氧化铝的孔径分布为0.1-5nm；以及The pore size distribution of the low pore size alumina is 0.1-5nm; and
高孔容氧化铝和低孔径氧化铝的质量比为1：0.1-10。The mass ratio of high pore volume alumina and low pore diameter alumina is 1:0.1-10.
进一步，所述固态氧化铝、分散剂、润湿剂、粘结剂、增稠剂、消泡剂、纯水的质量份比值依次为1：0.001-0.01：0.003-0.009：0.01-0.08：0.005-0.015：0-0.06：1-2.5。Further, the mass ratio of the solid alumina, dispersant, wetting agent, binder, thickener, defoamer, and pure water is 1:0.001-0.01:0.003-0.009:0.01-0.08:0.005. -0.015: 0-0.06: 1-2.5.
进一步，所述分散剂包括有硅酸盐类、碱金属磷酸盐类、有机分散剂、钠盐分散剂、铵盐分散剂中的一种或几种；其中所述有硅酸盐类包括水玻璃；所 述碱金属磷酸盐类包括三聚磷酸钠、六偏磷酸钠、焦磷酸钠中的至少一种；所述有机分散剂包括三乙基己基磷酸、十二烷基硫酸钠、甲基戊醇、纤维素衍生物、聚丙烯酰胺、古尔胶、脂肪酸聚乙二醇酯中的一种或几种。Further, the dispersant includes one or more of silicates, alkali metal phosphates, organic dispersants, sodium salt dispersants, and ammonium salt dispersants; wherein the silicates include water glass; The alkali metal phosphates include at least one of sodium tripolyphosphate, sodium hexametaphosphate, and sodium pyrophosphate; the organic dispersant includes triethylhexyl phosphoric acid, sodium lauryl sulfate, and methylpentanol , Cellulose derivatives, polyacrylamide, Guer gum, fatty acid polyethylene glycol ester, one or more of them.
进一步，所述润湿剂包括阴离子型表面活性剂、非离子型表面活性剂、中性表面活性剂中的至少一种。Further, the wetting agent includes at least one of anionic surfactants, nonionic surfactants, and neutral surfactants.
进一步，所述粘结剂包括水性粘结剂。Further, the binder includes an aqueous binder.
进一步，所述增稠剂包括羧甲基丙烯酸钠。Further, the thickener includes sodium carboxymethacrylate.
进一步，所述消泡剂包括异丙醇。Further, the defoamer includes isopropanol.
又一方面，本发明还提供了一种氧化铝陶瓷浆料的制备方法，即将固态氧化铝、分散剂、润湿剂、粘结剂、增稠剂、消泡剂、纯水搅拌混合，进行分散，形成所述氧化铝陶瓷浆料。In another aspect, the present invention also provides a method for preparing alumina ceramic slurry, which is to stir and mix solid alumina, dispersant, wetting agent, binder, thickener, defoamer, and pure water. Dispersed to form the alumina ceramic slurry.
另一方面，本发明还提供了一种锂电池隔膜，包括：PE膜、涂覆在PE膜上的氧化铝陶瓷浆料。On the other hand, the present invention also provides a lithium battery separator, which includes a PE film and an alumina ceramic slurry coated on the PE film.
本发明的有益效果是，本发明的氧化铝陶瓷浆料及制备方法、锂电池隔膜采用固态氧化铝与其他组分混合分散，形成氧化铝陶瓷浆料，以用于制备锂电池隔膜，大幅降低了隔膜的润湿时间，提高了电池的生产效率。The beneficial effect of the present invention is that the alumina ceramic slurry of the present invention and the preparation method thereof, the lithium battery diaphragm adopts solid alumina and other components to be mixed and dispersed to form alumina ceramic slurry for the preparation of lithium battery diaphragm, greatly reducing The wetting time of the separator is improved, and the production efficiency of the battery is improved.
本发明的其他特征和优点将在随后的说明书中阐述，并且，部分地从说明书中变得显而易见，或者通过实施本发明而了解。本发明的目的和其他优点在说明书、权利要求书以及附图中所特别指出的结构来实现和获得。Other features and advantages of the present invention will be described in the following description, and partly become obvious from the description, or understood by implementing the present invention. The purpose and other advantages of the present invention are realized and obtained by the structures specifically pointed out in the specification, claims and drawings.
为使本发明的上述目的、特征和优点能更明显易懂，下文特举较佳实施例，并配合所附附图，作详细说明如下。In order to make the above-mentioned objects, features and advantages of the present invention more obvious and understandable, preferred embodiments are described in detail below in conjunction with the accompanying drawings.
附图说明Description of the drawings
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将 对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following will briefly introduce the drawings that need to be used in the specific embodiments or the description of the prior art. Obviously, the appendix in the following description The drawings are some embodiments of the present invention. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative work.
图1是掺杂氧化铝电池与常规氧化铝电池的循环能力对比图；纵坐标是电池容量持率，横坐标是循环次数；Figure 1 is a comparison diagram of the cycle capacity of a doped alumina battery and a conventional alumina battery; the ordinate is the battery capacity holding rate, and the abscissa is the number of cycles;
图2是掺杂氧化铝电池与常规氧化铝电池的润湿时间对比图；Figure 2 is a comparison diagram of the wetting time of a doped alumina battery and a conventional alumina battery;
图3是高孔容氧化铝电池与常规氧化铝电池的循环能力对比图；纵坐标是电池容量持率，横坐标是循环次数；Figure 3 is a comparison diagram of the cycle capacity of a high pore volume alumina battery and a conventional alumina battery; the ordinate is the battery capacity retention rate, and the abscissa is the number of cycles;
图4是低孔径氧化铝电池与常规氧化铝电池的润湿时间对比图。Figure 4 is a comparison diagram of the wetting time of a low pore size alumina battery and a conventional alumina battery.
具体实施方式Detailed ways
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合附图对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings. Obviously, the described embodiments are part of the embodiments of the present invention, not all of them.的实施例。 Example. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work shall fall within the protection scope of the present invention.
高孔容氧化铝和低孔径氧化铝对循环能力和隔膜润湿时间的影响机理如下：高孔容可以提高氧化铝的孔隙率，储存更多的电解液，而低孔径可以增大毛细效应，提升氧化铝吸收电解液的速度，提升润湿效率。The mechanism of the influence of high pore volume alumina and low pore diameter alumina on cycle capacity and diaphragm wetting time is as follows: high pore volume can increase the porosity of alumina and store more electrolyte, while low pore volume can increase the capillary effect and enhance alumina absorption The speed of the electrolyte improves the wetting efficiency.
实施例1Example 1
本实施例1的一种氧化铝陶瓷浆料，包括以下原料：固态氧化铝、分散剂、润湿剂、粘结剂、增稠剂、消泡剂、纯水。The alumina ceramic slurry of Example 1 includes the following raw materials: solid alumina, dispersant, wetting agent, binder, thickener, defoamer, and pure water.
可选的，所述氧化铝陶瓷浆料的固含量为10-60％，优选30-40％。Optionally, the solid content of the alumina ceramic slurry is 10-60%, preferably 30-40%.
可选的，所述固态氧化铝、分散剂、润湿剂、粘结剂、增稠剂、消泡剂、 纯水的质量份比值依次为1：0.001-0.01：0.003-0.009：0.01-0.08：0.005-0.015：0-0.06：1-2.5。Optionally, the mass ratio of the solid alumina, dispersant, wetting agent, binder, thickener, defoamer, and pure water is 1:0.001-0.01:0.003-0.009:0.01-0.08. : 0.005-0.015: 0-0.06: 1-2.5.
优选的，所述固态氧化铝、分散剂、润湿剂、粘结剂、增稠剂、消泡剂、纯水的质量份比值依次为1：0.001-0.01：0.003-0.009：0.01-0.08：0.005-0.015：0-0.06：1-2.5。Preferably, the mass ratio of the solid alumina, dispersant, wetting agent, binder, thickener, defoamer, and pure water is 1:0.001-0.01:0.003-0.009:0.01-0.08 in order: 0.005-0.015: 0-0.06: 1-2.5.
可选的，所述固态氧化铝包括：高孔容氧化铝和/或低孔径氧化铝；所述高孔容氧化铝的孔容分布为0.4-3.0ml/g；所述低孔径氧化铝的孔径分布为0.1-5nm；以及高孔容氧化铝和低孔径氧化铝的质量比为1：0.1-10。Optionally, the solid alumina includes: high pore volume alumina and/or low pore diameter alumina; the pore volume distribution of the high pore volume alumina is 0.4-3.0 ml/g; the pore volume distribution of the low pore volume alumina is 0.1 -5nm; and the mass ratio of alumina with high pore volume and alumina with low pore volume is 1:0.1-10.
优选的，所述高孔容氧化铝的孔容分布为0.5-1.5ml/g，更优选为1ml/g；以及所述低孔径氧化铝的孔径分布为0.1-1nm，更优选为0.6nm。这种氧化铝的孔容和孔径分布范围既可以实现储存更多的电解液和提升润湿效率的作用，又便于工业生产。Preferably, the pore volume distribution of the high pore volume alumina is 0.5-1.5 ml/g, more preferably 1 ml/g; and the pore volume distribution of the low pore volume alumina is 0.1-1 nm, more preferably 0.6 nm. The pore volume and pore size distribution range of this alumina can not only store more electrolyte and improve the wetting efficiency, but also facilitate industrial production.
可选的，高孔容氧化铝和低孔径氧化铝的质量比为1：0.5-8，优选为1：1-5，可以使氧化铝陶瓷浆料的存液能力和润湿能力得到兼顾。Optionally, the mass ratio of high pore volume alumina and low pore diameter alumina is 1:0.5-8, preferably 1:1-5, so that the liquid storage capacity and wetting capacity of the alumina ceramic slurry can be balanced.
本实施例1的氧化铝陶瓷浆料将固态氧化铝采用低孔径氧化铝和/或高孔容氧化铝混合，并与其他组分混合分散，形成氧化铝陶瓷浆料，利用低孔径氧化铝可以增大毛细效应，提升氧化铝吸收电解液的速度，提升润湿效率；利用高孔容氧化铝可以提高氧化铝的孔隙率，储存更多的电解液，以提高锂电池的循环寿命，从而保证氧化铝陶瓷浆料的存液能力和润湿能力得到兼顾，大幅降低了隔膜的润湿时间，提高了电池的生产效率。The alumina ceramic slurry of Example 1 mixes solid alumina with low pore size alumina and/or high pore volume alumina, and mixes and disperses with other components to form alumina ceramic slurry, which can be enlarged by using low pore size alumina. Capillary effect increases the rate at which alumina absorbs electrolyte and improves wetting efficiency; using high pore volume alumina can increase the porosity of alumina and store more electrolyte to increase the cycle life of lithium batteries, thereby ensuring alumina ceramic slurry The liquid storage capacity and wetting capacity of the material are taken into account, which greatly reduces the wetting time of the separator and improves the production efficiency of the battery.
可选的，所述分散剂包括但不限于有硅酸盐类、碱金属磷酸盐类、有机分散剂、钠盐分散剂、铵盐分散剂中的一种或几种；其中所述有硅酸盐类包括但不限于水玻璃；所述碱金属磷酸盐类包括但不限于三聚磷酸钠、六偏磷酸钠、 焦磷酸钠中的至少一种；所述有机分散剂包括但不限于三乙基己基磷酸、十二烷基硫酸钠、甲基戊醇、纤维素衍生物、聚丙烯酰胺、古尔胶、脂肪酸聚乙二醇酯中的一种或几种。分散剂的作用主要是将固态氧化铝在溶剂中均匀分散，固态氧化铝在制作过程中存在一些残存的官能团(如-OH)，会与部分的分散剂发生副反应，产生团聚。Optionally, the dispersant includes, but is not limited to, one or more of silicates, alkali metal phosphates, organic dispersants, sodium salt dispersants, and ammonium salt dispersants; wherein the dispersants are silicates. Types include but are not limited to water glass; the alkali metal phosphates include but are not limited to at least one of sodium tripolyphosphate, sodium hexametaphosphate, and sodium pyrophosphate; the organic dispersant includes, but is not limited to, triethyl One or more of hexyl phosphoric acid, sodium lauryl sulfate, methylpentanol, cellulose derivatives, polyacrylamide, Guer gum, and fatty acid polyethylene glycol esters. The function of the dispersant is mainly to uniformly disperse the solid alumina in the solvent. There are some residual functional groups (such as -OH) during the production of solid alumina, which will cause side reactions with part of the dispersant and cause agglomeration.
可选的，所述润湿剂包括但不限于阴离子型表面活性剂、非离子型表面活性剂、中性表面活性剂中的至少一种。润湿剂的主要作用是在不影响循环能力和润湿时间的前提下，降低氧化铝陶瓷浆料的表面张力，使氧化铝陶瓷浆料能够涂覆在隔膜上。Optionally, the wetting agent includes but is not limited to at least one of anionic surfactants, nonionic surfactants, and neutral surfactants. The main function of the wetting agent is to reduce the surface tension of the alumina ceramic slurry without affecting the circulation capacity and wetting time, so that the alumina ceramic slurry can be coated on the diaphragm.
可选的，所述粘结剂包括但不限于水性粘结剂，例如但不限于丙烯酸类粘结剂。粘结剂的主要作用是在不影响循环能力和润湿时间的前提下，将氧化铝陶瓷浆料与隔膜粘结在一起，防止氧化铝陶瓷浆料脱落，提高隔膜的稳定性。Optionally, the adhesive includes but is not limited to an aqueous adhesive, such as but not limited to an acrylic adhesive. The main function of the binder is to bond the alumina ceramic slurry to the diaphragm without affecting the cycle capacity and wetting time, to prevent the alumina ceramic slurry from falling off, and to improve the stability of the diaphragm.
可选的，所述增稠剂包括但不限于羧甲基丙烯酸钠。增稠剂的作用主要是调节氧化铝陶瓷浆料的粘度，确保浆料的流平且避免浆料沉降过快，增稠剂的触变指数要高，高剪切力的情况下粘度变稀。同时还要保证不影响循环能力、润湿时间。Optionally, the thickener includes, but is not limited to, sodium carboxymethacrylate. The role of the thickener is mainly to adjust the viscosity of the alumina ceramic slurry, to ensure the smoothness of the slurry and to avoid the slurry from settling too fast. The thixotropic index of the thickener should be high, and the viscosity will become thin under high shearing force. . At the same time, it must be ensured that the circulation capacity and wetting time are not affected.
可选的，所述消泡剂包括但不限于异丙醇。消泡剂的作用主要是降低氧化铝陶瓷浆料中的气泡数量，以避免与浆料中的其他成分发生反应。Optionally, the defoamer includes but is not limited to isopropanol. The main function of the defoamer is to reduce the number of bubbles in the alumina ceramic slurry to avoid reaction with other components in the slurry.
实施例2Example 2
在实施例1的基础上，本实施例2还提供了一种氧化铝陶瓷浆料的制备方法，即将固态氧化铝、分散剂、润湿剂、粘结剂、增稠剂、消泡剂、纯水搅拌混合，进行分散，形成所述氧化铝陶瓷浆料。On the basis of Example 1, this Example 2 also provides a preparation method of alumina ceramic slurry, that is, solid alumina, dispersant, wetting agent, binder, thickener, defoamer, Pure water is stirred and mixed for dispersion to form the alumina ceramic slurry.
可选的，所述分散的方式包括采用双行星或砂磨机进行高速分散。Optionally, the dispersion method includes high-speed dispersion using a double planetary or sand mill.
关于氧化铝陶瓷浆料的组分含量和具体实施过程参见实施例1中的相关论述，在此不再赘述。Regarding the component content and specific implementation process of the alumina ceramic slurry, refer to the relevant discussion in Example 1, and will not be repeated here.
实施例3Example 3
在实施例1和2的基础上，本实施例3还提供了一种锂电池隔膜，包括：PE膜、涂覆在PE膜上的氧化铝陶瓷浆料。On the basis of Embodiments 1 and 2, this Embodiment 3 also provides a lithium battery separator, which includes a PE film and an alumina ceramic slurry coated on the PE film.
可选的，所述PE膜为12μm，氧化铝陶瓷浆料的涂覆厚度为2μm，且涂覆两层，即规格为12μm+2μm+2μm的掺杂氧化铝电池或高孔容氧化铝电池或低孔径氧化铝电池。Optionally, the PE film is 12μm, the coating thickness of the alumina ceramic slurry is 2μm, and two layers are coated, that is, a doped alumina battery or a high-porosity alumina battery or a low-volume alumina battery with a specification of 12μm+2μm+2μm. Alumina cell with pore size.
关于氧化铝陶瓷浆料的组分含量和具体实施过程参见实施例1中的相关论述，在此不再赘述。Regarding the component content and specific implementation process of the alumina ceramic slurry, refer to the relevant discussion in Example 1, and will not be repeated here.
实施例4Example 4
通过特定的检测设备选用孔容为1.0ml/g的高孔容氧化铝和孔径为1nm的低孔径氧化铝，配置50kg的掺杂氧化铝陶瓷浆料。A high pore volume alumina with a pore volume of 1.0 ml/g and a low pore diameter alumina with a pore diameter of 1 nm are selected through specific detection equipment, and 50 kg of doped alumina ceramic slurry is configured.
(1)先将6kg的1nm孔径的低孔径氧化铝与12.5kg孔容为1.0ml/g的高孔容氧化铝进行砂磨混合；(1) First, 6kg of 1nm pore size low pore size alumina and 12.5kg pore size of 1.0ml/g high pore volume alumina are sand-milled and mixed;
(2)先在搅拌罐中添加20.5kg纯水，然后在水中添加0.093kg的钠盐分散剂进行搅拌分散；(2) First add 20.5kg of pure water to the stirring tank, and then add 0.093kg of sodium salt dispersant in the water for stirring and dispersing;
(3)在再添加分散剂后的水中加入18.5kg的混合氧化铝，进行搅拌分散；(3) Add 18.5kg of mixed alumina to the water after adding the dispersant, and stir and disperse;
(4)再加入4.8kg的羧甲基丙烯酸钠溶液，进行搅拌砂磨；(4) Add 4.8 kg of sodium carboxymethacrylate solution and stir and sand;
(5)再加入5.5kg的丙烯酸类的粘结剂，进行搅拌；(5) Add 5.5 kg of acrylic binder and stir;
(6)再加入0.56kg的润湿剂溶液，进行搅拌分散；(6) Add 0.56kg of wetting agent solution and stir and disperse;
(7)消泡剂未加；(7) No defoamer added;
(8)配置掺杂氧化铝陶瓷浆料后采用12μm的PE膜，涂覆2μm，形成规 格为12μm+2μm+2μm的掺杂氧化铝电池。(8) After disposing the doped alumina ceramic slurry, use a 12 m PE film and coat it with 2 m to form a doped alumina battery with a specification of 12 m + 2 m + 2 m.
实施例5Example 5
选用孔容为1.0ml/g的高孔容氧化铝，配置50kg的高孔容氧化铝陶瓷浆料。Select high pore volume alumina with a pore volume of 1.0 ml/g, and configure 50 kg of high pore volume alumina ceramic slurry.
(1)先在搅拌罐中添加20.5kg纯水，然后在水中添加0.093kg的钠盐分散剂进行搅拌分散；(1) First add 20.5kg of pure water to the stirring tank, and then add 0.093kg of sodium salt dispersant in the water for stirring and dispersing;
(2)在再添加分散剂后的水中加入18.5kg的高孔容氧化铝，进行搅拌分散；(2) Add 18.5kg of high pore volume alumina to the water after adding the dispersant, and stir and disperse;
(3)再加入4.8kg的羧甲基丙烯酸钠溶液，进行搅拌砂磨；(3) Add 4.8 kg of sodium carboxymethacrylate solution and stir and sand;
(4)再加入5.5kg的丙烯酸类的粘结剂，进行搅拌；(4) Add 5.5kg of acrylic binder and stir;
(5)再加入0.56kg的润湿剂溶液，进行搅拌分散；(5) Add 0.56kg of wetting agent solution and stir and disperse;
(6)消泡剂未加；(6) No defoamer added;
(7)浆料配置后采用12μm的PE膜，涂覆规格为12μm+2μm+2μm，制成高孔容氧化铝电池。(7) After the slurry is configured, a 12μm PE film is used, and the coating specification is 12μm+2μm+2μm to make a high pore volume alumina battery.
实施例6Example 6
选用孔径为1nm的低孔径氧化铝，配置50kg的低孔径氧化铝陶瓷浆料，然后进行隔膜涂覆应用到电池中。Select low-pore alumina with a pore diameter of 1nm, configure 50kg of low-pore alumina ceramic slurry, and then apply diaphragm coating to the battery.
(1)先在搅拌罐中添加20.5kg纯水，然后在水中添加0.093kg的钠盐分散剂进行搅拌分散；(1) First add 20.5kg of pure water to the stirring tank, and then add 0.093kg of sodium salt dispersant in the water for stirring and dispersing;
(2)在再添加分散剂后的水中加入18.5kg的低孔径氧化铝，进行搅拌分散；(2) Add 18.5kg of low pore alumina to the water after adding the dispersant, and stir and disperse;
(3)再加入4.8kg的羧甲基丙烯酸钠溶液，进行搅拌砂磨；(3) Add 4.8 kg of sodium carboxymethacrylate solution and stir and sand;
(4)再加入5.5kg的丙烯酸类的粘结剂，进行搅拌；(4) Add 5.5kg of acrylic binder and stir;
(5)再加入0.56kg的润湿剂溶液，进行搅拌分散；(5) Add 0.56kg of wetting agent solution and stir and disperse;
(6)消泡剂未加；(6) No defoamer added;
(7)浆料配置后采用12μm的PE膜，涂覆规格为12μm+2μm+2μm，制成低孔径氧化铝电池。(7) After the slurry is configured, a 12μm PE film is used, and the coating specification is 12μm+2μm+2μm to make a low-pore alumina battery.
实施例7Example 7
选用孔容为0.4ml/g的高孔容氧化铝和孔径为0.1nm的低孔径氧化铝，配置掺杂氧化铝陶瓷浆料。A high pore volume alumina with a pore volume of 0.4 ml/g and a low pore diameter alumina with a pore volume of 0.1 nm are selected to configure the doped alumina ceramic slurry.
(1)先将1kg的0.1nm孔径的低孔径氧化铝与9kg孔容为0.1ml/g的高孔容氧化铝进行砂磨混合；(1) First, 1kg of 0.1nm pore size low pore size alumina and 9kg pore size of 0.1ml/g high pore volume alumina are sand-milled and mixed;
(2)先在搅拌罐中添加10kg纯水，然后在水中添加0.01kg的钠盐分散剂进行搅拌分散；(2) First add 10kg of pure water to the stirring tank, and then add 0.01kg of sodium salt dispersant to the water for stirring and dispersion;
(3)在再添加分散剂后的水中加入10kg的混合氧化铝，进行搅拌分散；(3) Add 10 kg of mixed alumina to the water after adding the dispersant, and stir and disperse;
(4)再加入0.05kg的羧甲基丙烯酸钠溶液的增稠剂，进行搅拌砂磨；(4) Add 0.05kg of the thickener of sodium carboxymethacrylate solution and stir and sand;
(5)再加入0.1kg的丙烯酸类的粘结剂，进行搅拌；(5) Add 0.1kg of acrylic binder and stir;
(6)再加入0.03kg的润湿剂溶液，进行搅拌分散；(6) Add 0.03kg of wetting agent solution and stir and disperse;
(7)消泡剂未加；(7) No defoamer added;
(8)配置掺杂氧化铝陶瓷浆料后采用12μm的PE膜，涂覆2μm，形成规格为12μm+2μm+2μm的掺杂氧化铝电池。(8) After configuring the doped alumina ceramic slurry, use a 12 μm PE film and coat it with 2 μm to form a doped alumina battery with a specification of 12 μm+2 μm+2 μm.
实施例8Example 8
选用孔容为3ml/g的高孔容氧化铝和孔径为5nm的低孔径氧化铝，配置掺杂氧化铝陶瓷浆料。A high pore volume alumina with a pore volume of 3 ml/g and a low pore diameter alumina with a pore volume of 5 nm are selected to configure the doped alumina ceramic slurry.
(1)先将9kg的5nm孔径的低孔径氧化铝与1kg孔容为3ml/g的高孔容氧化铝进行砂磨混合；(1) Firstly, 9kg of 5nm pore size low pore size alumina and 1kg pore volume of 3ml/g high pore volume alumina are sand-milled and mixed;
(2)先在搅拌罐中添加25kg纯水，然后在水中添加0.1kg的钠盐分散剂 进行搅拌分散；(2) First add 25kg of pure water to the stirring tank, and then add 0.1kg of sodium salt dispersant to the water for stirring and dispersing;
(3)在再添加分散剂后的水中加入10kg的混合氧化铝，进行搅拌分散；(3) Add 10 kg of mixed alumina to the water after adding the dispersant, and stir and disperse;
(4)再加入0.15kg的羧甲基丙烯酸钠溶液的增稠剂，进行搅拌砂磨；(4) Add 0.15 kg of the thickener of sodium carboxymethacrylate solution, and stir and sand;
(5)再加入0.8kg的丙烯酸类的粘结剂，进行搅拌；(5) Add 0.8kg of acrylic binder and stir;
(6)再加入0.09kg的润湿剂溶液，进行搅拌分散；(6) Add 0.09kg of wetting agent solution and stir and disperse;
(7)消泡剂0.6kg；(7) 0.6kg of defoamer;
(8)配置掺杂氧化铝陶瓷浆料后采用12μm的PE膜，涂覆2μm，形成规格为12μm+2μm+2μm的掺杂氧化铝电池。(8) After configuring the doped alumina ceramic slurry, use a 12 μm PE film and coat it with 2 μm to form a doped alumina battery with a specification of 12 μm+2 μm+2 μm.
实施例9Example 9
选用孔容为1.5ml/g的高孔容氧化铝和孔径为3nm的低孔径氧化铝，配置掺杂氧化铝陶瓷浆料。A high pore volume alumina with a pore volume of 1.5 ml/g and a low pore diameter alumina with a pore volume of 3 nm are selected to configure the doped alumina ceramic slurry.
(1)先将5kg的3nm孔径的低孔径氧化铝与5kg孔容为1.5ml/g的高孔容氧化铝进行砂磨混合；(1) First, sand and mix 5kg of low pore size alumina with 3nm pore size and 5kg of high pore volume alumina with pore volume of 1.5ml/g;
(2)先在搅拌罐中添加15kg纯水，然后在水中添加0.06kg的钠盐分散剂进行搅拌分散；(2) First add 15kg of pure water to the stirring tank, and then add 0.06kg of sodium salt dispersant in the water for stirring and dispersing;
(3)在再添加分散剂后的水中加入10kg的混合氧化铝，进行搅拌分散；(3) Add 10 kg of mixed alumina to the water after adding the dispersant, and stir and disperse;
(4)再加入0.1kg的羧甲基丙烯酸钠溶液的增稠剂，进行搅拌砂磨；(4) Add 0.1kg of the thickener of sodium carboxymethacrylate solution, and stir and sand;
(5)再加入0.4kg的丙烯酸类的粘结剂，进行搅拌；(5) Add 0.4kg of acrylic binder and stir;
(6)再加入0.06kg的润湿剂溶液，进行搅拌分散；(6) Add 0.06kg of wetting agent solution and stir and disperse;
(7)消泡剂0.3kg；(7) 0.3kg of defoamer;
(8)配置掺杂氧化铝陶瓷浆料后采用12μm的PE膜，涂覆2μm，形成规格为12μm+2μm+2μm的掺杂氧化铝电池。(8) After configuring the doped alumina ceramic slurry, use a 12 μm PE film and coat it with 2 μm to form a doped alumina battery with a specification of 12 μm+2 μm+2 μm.
对比例1Comparative example 1
选用孔容为0.3ml/g、孔径为8nm的常规氧化铝，配置50kg的常规氧化铝陶瓷浆料。A conventional alumina with a pore volume of 0.3ml/g and a pore diameter of 8nm is selected, and 50kg of conventional alumina ceramic slurry is configured.
(1)先在搅拌罐中添加20.5kg纯水，然后在水中添加0.093kg的钠盐分散剂进行搅拌分散；(1) First add 20.5kg of pure water to the stirring tank, and then add 0.093kg of sodium salt dispersant in the water for stirring and dispersing;
(2)在再添加分散剂后的水中加入18.5kg的常规氧化铝，进行搅拌分散。(2) Add 18.5 kg of conventional alumina to the water after adding the dispersant, and stir and disperse.
(3)再加入4.8kg的羧甲基丙烯酸钠溶液，进行搅拌砂磨(3) Add 4.8kg of sodium carboxymethacrylate solution and stir and sand
(4)再加入5.5kg的丙烯酸类的粘结剂，进行搅拌；(4) Add 5.5kg of acrylic binder and stir;
(5)再加入0.56kg的润湿剂溶液，进行搅拌分散；(5) Add 0.56kg of wetting agent solution and stir and disperse;
(6)消泡剂未加；(6) No defoamer added;
(7)浆料配置后采用12μm的PE膜，涂覆2μm的常规氧化铝陶瓷浆料，形成规格为12μm+2μm+2μm的常规氧化铝电池。(7) After the slurry is configured, a PE film of 12 μm is used, and a conventional alumina ceramic slurry of 2 μm is coated to form a conventional alumina battery with a specification of 12 μm + 2 μm + 2 μm.
对比例2Comparative example 2
选用孔容为0.3ml/g的常规氧化铝，配置50kg的常规氧化铝陶瓷浆料。Choose conventional alumina with a pore volume of 0.3ml/g, and configure 50kg of conventional alumina ceramic slurry.
(1)先在搅拌罐中添加20.5kg纯水，然后在水中添加0.093kg的钠盐分散剂进行搅拌分散；(1) First add 20.5kg of pure water to the stirring tank, and then add 0.093kg of sodium salt dispersant in the water for stirring and dispersing;
(2)在再添加分散剂后的水中加入18.5kg的常规氧化铝，进行搅拌分散；(2) Add 18.5kg of conventional alumina to the water after adding the dispersant, and stir and disperse;
(3)再加入4.8kg的羧甲基丙烯酸钠溶液，进行搅拌砂磨；(3) Add 4.8 kg of sodium carboxymethacrylate solution and stir and sand;
(4)再加入5.5kg的丙烯酸类的粘结剂，进行搅拌；(4) Add 5.5kg of acrylic binder and stir;
(5)再加入0.56kg的润湿剂溶液，进行搅拌分散；(5) Add 0.56kg of wetting agent solution and stir and disperse;
(6)消泡剂未加；(6) No defoamer added;
(7)浆料配置后采用12μm的PE膜，涂覆2μm的常规氧化铝陶瓷浆料，形成规格为12μm+2μm+2μm的常规氧化铝电池。(7) After the slurry is configured, a PE film of 12 μm is used, and a conventional alumina ceramic slurry of 2 μm is coated to form a conventional alumina battery with a specification of 12 μm + 2 μm + 2 μm.
对比例3Comparative example 3
选用孔径为10nm的常规氧化铝，配置50kg的常规氧化铝陶瓷浆料，然后进行隔膜涂覆应用到电池中。Select conventional alumina with a pore diameter of 10 nm, configure 50 kg of conventional alumina ceramic slurry, and then apply diaphragm coating to the battery.
(1)先在搅拌罐中添加20.5kg纯水，然后在水中添加0.093kg的钠盐分散剂进行搅拌分散；(1) First add 20.5kg of pure water to the stirring tank, and then add 0.093kg of sodium salt dispersant in the water for stirring and dispersing;
(2)在再添加分散剂后的水中加入18.5kg的常规氧化铝，进行搅拌分散；(2) Add 18.5kg of conventional alumina to the water after adding the dispersant, and stir and disperse;
(3)再加入4.8kg的羧甲基丙烯酸钠溶液，进行搅拌砂磨；(3) Add 4.8 kg of sodium carboxymethacrylate solution and stir and sand;
(4)再加入5.5kg的丙烯酸类的粘结剂，进行搅拌；(4) Add 5.5kg of acrylic binder and stir;
(5)再加入0.56kg的润湿剂溶液，进行搅拌分散；(5) Add 0.56kg of wetting agent solution and stir and disperse;
(6)消泡剂未加；(6) No defoamer added;
(7)浆料配置后采用12μm的PE膜，涂覆规格为12μm+2μm+2μm，制成常规氧化铝电池。(7) After the slurry is configured, a 12μm PE film is used, and the coating specification is 12μm+2μm+2μm to make a conventional alumina battery.
实施例10Example 10
本实施例10对实施例4-6、对比例1-3中的浆料涂覆制备电池进行测试，以检测其隔膜的循环能力和润湿时间，结果如表1所示。In Example 10, the batteries prepared by coating the slurry in Examples 4-6 and Comparative Examples 1-3 were tested to detect the cycle capacity and wetting time of the separator. The results are shown in Table 1.
表1 各浆料涂覆制备电池的性能对比Table 1 Performance comparison of batteries prepared by various slurry coatings
实验组test group 实施例4Example 4 实施例5Example 5 实施例6Example 6 对比例1Comparative example 1 对比例2Comparative example 2 对比例3Comparative example 3
润湿时间/SWetting time/S 1515 -- 1010 3030 -- 3030
循环能力/％(10次)Circulation capacity/% (10 times) 99.5-10099.5-100 99.5-10099.5-100 -- 97.5-9897.5-98 97.5-9897.5-98 --
循环能力/％(20次)Circulation capacity/% (20 times) 98.5-9998.5-99 98.5-9998.5-99 -- 96.5-9796.5-97 96.5-9796.5-97 --
循环能力/％(30次)Circulation capacity/% (30 times) 98-98.598-98.5 98-98.598-98.5 -- 96-96.596-96.5 96-96.596-96.5 --
图1是掺杂氧化铝电池与常规氧化铝电池的循环能力对比图。Figure 1 is a comparison diagram of the cycle capacity of a doped alumina battery and a conventional alumina battery.
图2是掺杂氧化铝电池与常规氧化铝电池的润湿时间对比图。Figure 2 is a comparison chart of the wetting time of a doped alumina battery and a conventional alumina battery.
(1)见图1和图2，结合实施例4和对比例1，本案的掺杂氧化铝电池的润湿时间为正常氧化铝电池的一半，其循环能力高于正常氧化铝电池。究其原因在于，采用高孔容氧化铝和低孔径氧化铝为主要组分，并结合其他组分混合 分散，提高了固态氧化铝的孔容，使其孔隙率提升，存电解液的数量增加，提升了电解液的循环能力，固态氧化铝孔径的变小，使固态氧化铝的毛细效应增强，吸液能力更快，提升了电解液的润湿能力，两种固态氧化铝的掺杂既提升了锂电池的循环性能，又提升了锂电池隔膜的润湿能力。(1) Figures 1 and 2, combined with Example 4 and Comparative Example 1, the wetting time of the doped alumina battery in this case is half of that of the normal alumina battery, and its cycle capacity is higher than that of the normal alumina battery. The reason is that the use of high pore volume alumina and low pore diameter alumina as the main components, combined with other components to mix and disperse, increase the pore volume of solid alumina, increase its porosity, and increase the amount of stored electrolyte. The circulation capacity of the electrolyte is improved, the pore diameter of the solid alumina is reduced, the capillary effect of the solid alumina is enhanced, the liquid absorption capacity is faster, and the wetting ability of the electrolyte is improved. The cycle performance of the lithium battery improves the wetting ability of the lithium battery separator.
图3是高孔容氧化铝电池与常规氧化铝电池的循环能力对比图。Figure 3 is a comparison diagram of the cycle capacity of a high pore volume alumina battery and a conventional alumina battery.
(2)如图3所示，结合实施例5和对比例2，本案的高孔氧化铝电池的循环能力高于常规氧化铝电池。主要是因为高孔容氧化铝提高了固态氧化铝的孔容，使其孔隙率提升，存电解液的数量增加，提升了电解液的循环能力。(2) As shown in Figure 3, combining Example 5 and Comparative Example 2, the cycle capacity of the high-porosity alumina battery in this case is higher than that of the conventional alumina battery. The main reason is that high pore volume alumina increases the pore volume of solid alumina, increases its porosity, increases the amount of electrolyte stored, and improves the circulation capacity of the electrolyte.
图4是低孔径氧化铝电池与常规氧化铝电池的润湿时间对比图。Figure 4 is a comparison diagram of the wetting time of a low pore size alumina battery and a conventional alumina battery.
(3)如图4所示，结合实施例6和对比例3，本案的低孔径氧化铝电池的润湿时间为10S，远低于常规氧化铝电池的30S。主要是因为用低孔径氧化铝可以增大毛细效应，提升氧化铝吸收电解液的速度，提升润湿效率。(3) As shown in Figure 4, combining Example 6 and Comparative Example 3, the wetting time of the low-pore alumina battery in this case is 10S, which is much lower than the 30S of the conventional alumina battery. The main reason is that the use of low-pore alumina can increase the capillary effect, increase the rate at which the alumina absorbs the electrolyte, and improve the wetting efficiency.
综上所述，本高润湿长循环的氧化铝陶瓷浆料及制备方法、锂电池隔膜通过固态氧化铝采用低孔径氧化铝和/或高孔容氧化铝混合，并与其他组分混合分散，形成氧化铝陶瓷浆料，高孔容氧化铝可以提高氧化铝的孔隙率，储存更多的电解液，以提高锂电池的循环寿命；低孔径氧化铝可以增大毛细效应，提升氧化铝吸收电解液的速度，提升润湿效率，大幅降低了隔膜的润湿时间，从而提高了电池的生产效率，当高孔容氧化铝与低孔径氧化铝混合使用时，还可以时电池的存液能力和润湿能力得到兼顾，达到高润湿和长循环的效果。In summary, the high-wetting long-cycle alumina ceramic slurry and preparation method, the lithium battery separator is mixed with low-pore alumina and/or high-porosity alumina through solid alumina, and mixed and dispersed with other components to form Alumina ceramic slurry, high pore volume alumina can increase the porosity of alumina and store more electrolyte to increase the cycle life of lithium batteries; low pore alumina can increase the capillary effect and increase the rate at which alumina absorbs electrolyte , Improve the wetting efficiency, greatly reduce the wetting time of the separator, thereby improving the production efficiency of the battery. When high pore volume alumina is mixed with low pore diameter alumina, the battery's liquid storage capacity and wetting ability can also be taken into account. , To achieve the effect of high wetting and long circulation.
以上述依据本发明的理想实施例为启示，通过上述的说明内容，相关工作人员完全可以在不偏离本项发明技术思想的范围内，进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容，必须要根据权利要求范围来确定其技术性范围。Taking the above-mentioned ideal embodiment according to the present invention as enlightenment, through the above-mentioned description content, relevant workers can make various changes and modifications without departing from the scope of the technical idea of the present invention. The technical scope of the present invention is not limited to the content of the description, and the technical scope must be determined according to the scope of the claims.

Claims (10)

  1. 一种氧化铝陶瓷浆料，其特征在于，包括以下原料：An alumina ceramic slurry is characterized in that it comprises the following raw materials:
    固态氧化铝、分散剂、润湿剂、粘结剂、增稠剂、消泡剂、纯水。Solid alumina, dispersant, wetting agent, binder, thickener, defoamer, pure water.
  2. 根据权利要求1所述的氧化铝陶瓷浆料，其特征在于，The alumina ceramic slurry of claim 1, wherein:
    所述固态氧化铝包括：高孔容氧化铝和/或低孔径氧化铝；其中The solid alumina includes: high pore volume alumina and/or low pore diameter alumina; wherein
    所述高孔容氧化铝的孔容分布为0.4-3.0ml/g；以及The pore volume distribution of the high pore volume alumina is 0.4-3.0 ml/g; and
    所述低孔径氧化铝的孔径分布为0.1-5nm。The pore size distribution of the low pore size alumina is 0.1-5 nm.
    高孔容氧化铝和低孔径氧化铝的质量比为1：0.1-10。The mass ratio of high pore volume alumina and low pore diameter alumina is 1:0.1-10.
  3. 根据权利要求1或2所述的氧化铝陶瓷浆料，其特征在于，The alumina ceramic slurry of claim 1 or 2, wherein:
    所述固态氧化铝、分散剂、润湿剂、粘结剂、增稠剂、消泡剂、纯水的质量份比值依次为1：0.001-0.01：0.003-0.009：0.01-0.08：0.005-0.015：0-0.06：1-2.5。The mass ratios of the solid alumina, dispersant, wetting agent, binder, thickener, defoamer, and pure water are 1:0.001-0.01:0.003-0.009:0.01-0.08:0.005-0.015. :0-0.06: 1-2.5.
  4. 根据权利要求1所述的氧化铝陶瓷浆料，其特征在于，The alumina ceramic slurry of claim 1, wherein:
    所述分散剂包括有硅酸盐类、碱金属磷酸盐类、有机分散剂、钠盐分散剂、铵盐分散剂中的一种或几种；其中The dispersant includes one or more of silicates, alkali metal phosphates, organic dispersants, sodium salt dispersants, and ammonium salt dispersants;
    所述有硅酸盐类包括水玻璃；The silicates include water glass;
    所述碱金属磷酸盐类包括三聚磷酸钠、六偏磷酸钠、焦磷酸钠中的至少一种；The alkali metal phosphates include at least one of sodium tripolyphosphate, sodium hexametaphosphate, and sodium pyrophosphate;
    所述有机分散剂包括三乙基己基磷酸、十二烷基硫酸钠、甲基戊醇、纤维素衍生物、聚丙烯酰胺、古尔胶、脂肪酸聚乙二醇酯中的一种或几种。The organic dispersant includes one or more of triethylhexyl phosphoric acid, sodium lauryl sulfate, methylpentanol, cellulose derivatives, polyacrylamide, Guer gum, and fatty acid polyethylene glycol esters .
  5. 根据权利要求1所述的氧化铝陶瓷浆料，其特征在于，The alumina ceramic slurry of claim 1, wherein:
    所述润湿剂包括阴离子型表面活性剂、非离子型表面活性剂、中性表面活性剂中的至少一种。The wetting agent includes at least one of anionic surfactants, nonionic surfactants, and neutral surfactants.
  6. 根据权利要求1所述的氧化铝陶瓷浆料，其特征在于，The alumina ceramic slurry of claim 1, wherein:
    所述粘结剂包括水性粘结剂。The binder includes an aqueous binder.
  7. 根据权利要求1所述的氧化铝陶瓷浆料，其特征在于，The alumina ceramic slurry of claim 1, wherein:
    所述增稠剂包括羧甲基丙烯酸钠。The thickener includes sodium carboxymethacrylate.
  8. 根据权利要求1所述的氧化铝陶瓷浆料，其特征在于，The alumina ceramic slurry of claim 1, wherein:
    所述消泡剂包括异丙醇。The defoamer includes isopropanol.
  9. 一种氧化铝陶瓷浆料的制备方法，其特征在于，A method for preparing alumina ceramic slurry, characterized in that:
    将固态氧化铝、分散剂、润湿剂、粘结剂、增稠剂、消泡剂、纯水搅拌混合，进行分散，形成所述氧化铝陶瓷浆料。The solid alumina, dispersant, wetting agent, binder, thickener, defoamer, and pure water are stirred and mixed for dispersion to form the alumina ceramic slurry.
  10. 一种锂电池隔膜，其特征在于，包括：A lithium battery separator, characterized in that it comprises:
    PE膜、涂覆在PE膜上的氧化铝陶瓷浆料。PE film, alumina ceramic slurry coated on PE film.
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