WO2023198031A1 - 一种电池用固含量稳定的无机氧化物固态电解质分散液及其制备方法和应用 - Google Patents

一种电池用固含量稳定的无机氧化物固态电解质分散液及其制备方法和应用 Download PDF

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WO2023198031A1
WO2023198031A1 PCT/CN2023/087527 CN2023087527W WO2023198031A1 WO 2023198031 A1 WO2023198031 A1 WO 2023198031A1 CN 2023087527 W CN2023087527 W CN 2023087527W WO 2023198031 A1 WO2023198031 A1 WO 2023198031A1
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inorganic oxide
dispersion
solid electrolyte
solid content
oxide solid
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PCT/CN2023/087527
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English (en)
French (fr)
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邱纪亮
杨琪
郭鲁新
俞会根
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北京卫蓝新能源科技有限公司
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Publication of WO2023198031A1 publication Critical patent/WO2023198031A1/zh

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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
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
    • H01M10/0563—Liquid materials, e.g. for Li-SOCl2 cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
    • B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
    • B02C17/00—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls
    • B02C17/10—Disintegrating by tumbling mills, i.e. mills having a container charged with the material to be disintegrated with or without special disintegrating members such as pebbles or balls with one or a few disintegrating members arranged in the container
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • 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 invention relates to the technical field of lithium batteries, and in particular to an inorganic oxide solid electrolyte dispersion with stable solid content for batteries and its preparation method and application.
  • inorganic solid electrolytes that can replace flammable organic electrolytes into batteries especially inorganic oxide solid electrolytes, usually includes application in pole piece modification and separator modification, which can improve battery safety performance.
  • the inorganic oxide solid electrolyte easily settles at the bottom of the container, resulting in uneven solid content in the upper and lower layers of the dispersion, and the material
  • the unstable solid content directly results in inaccurate loading values during feeding, causing difficulties in production.
  • solids may even settle and agglomerate at the bottom of the container, causing the The material cannot be redispersed evenly or even used.
  • the inherent Instability is often accompanied by unstable particle size, and poor dispersion particle size stability can easily lead to poor results during use.
  • the storage time is more than thirty days.
  • Long-term storage requires higher stability of the dispersion.
  • the solid content of the dispersion liquid used at this time is usually less than 10wt%, because the existing technology generally believes that low solid content helps to improve the solid content stability and particle size stability of the dispersion liquid.
  • the current method of use is to prepare and use immediately, which seriously affects the efficiency of actual large-scale production. The above problems seriously hinder the large-scale application of inorganic oxide solid electrolytes.
  • inorganic oxide solid electrolyte In order to use an inorganic oxide solid electrolyte, it is usually required that the solid content of the inorganic oxide solid electrolyte dispersion changes ⁇ 2% during transportation, storage, and loading.
  • the solid content of inorganic oxide solid electrolyte nanodispersions in the prior art is relatively low, usually less than 30 wt%, or even less than 10 wt%.
  • the greater the solvent content the higher the transportation cost, and if flammable and explosive organic solvents are used, the risk is higher. Therefore, low solid content dispersions generally have high transportation costs and high risks. If a dispersion with very low solid content is used during storage, a large amount of solvent will be required, increasing storage costs. When used, the solid content may be too low to be used with existing electrode material slurry formulas. Therefore, it is important to improve the solid content stability of inorganic oxide solid electrolyte nanodispersions while ensuring a certain solid content.
  • methods to improve the stability of the solid content of dispersions and prevent settlement mainly include adding dispersants, centrifugation, and preparing materials with special morphology.
  • CN112876901A discloses a water-dispersible functional ceramic ink, which is obtained by dispersing Li 7 La 3 Zr 2 O 12 powder mixture in a polyacrylamide aqueous solution dispersion medium, with a viscosity of 3 to 5 mPa ⁇ s and a surface tension of 55 to 65 mN/ m, ceramic ink has excellent stability Properties, 6 to 15g of Li 7 La 3 Zr 2 O 12 powder mixture is dispersed in every 100 mL of dispersion medium.
  • this invention because the solid content is too low, there are problems in transportation, storage, and use of the above-mentioned low solid content dispersion.
  • CN102760510B discloses a method to produce an ATO nanocrystal aqueous dispersion with high purity, high solid content, good transparency, excellent conductivity, stable storage, and non-agglomeration and non-sedimentation without using any additives.
  • this method after grinding with a sand mill and ultrasonically crushing and dispersing to prepare an ordinary ATO aqueous dispersion, the dispersion is centrifuged at high speed to obtain a supernatant with small particle size. This method believes that the stability of the dispersion can be improved at low solid content.
  • the advantage of this method is that it does not use any additives and accelerates the sedimentation of large particles through centrifugation.
  • the small particles in the supernatant that do not settle under centrifugation are stable under ordinary conditions and are not easy to settle.
  • the disadvantage is that the solid content of the supernatant after centrifugation is reduced, and the solids in the lower layer after centrifugation are easy to agglomerate. It needs to be broken through multiple stages to obtain the dispersion. The process is complicated and the efficiency of the entire process is low. Moreover, the dispersion prepared by this method has low solid content.
  • CN201810560205.3 discloses a method of using a dispersant combined with low-temperature centrifugation technology to prepare a Zn 2 TiO 4 dispersion with stable solid content.
  • the solid content gradient distribution occurs during the centrifugation process, and the overall solid content uniformity of the slurry is poor. It should be noted that even if a dispersant is used, the solid content stability of the dispersion cannot be completely guaranteed. The process of adjusting system stability often requires precise matching of various parameters in the system. Only adding dispersant cannot achieve the effect of long-term storage.
  • CN113964450A provides a battery separator coating liquid and a preparation method thereof.
  • the battery separator coating liquid contains ceramic nanowires with a diameter of 1 to 1000 nm and a length of 0.05 to 100 ⁇ m.
  • the uniform dispersion of nanowire dispersion requires in addition to the interaction between nanowires and nanowires.
  • the hydrogen bonding effect between the two requires the use of other additives and ceramic particles, making the formula complex.
  • CN202010494930.2 relates to a method for preparing a high mechanical strength solid electrolyte film.
  • the preparation method includes the following steps: prepare a solid electrolyte slurry, add the solid electrolyte and binder to the dispersion in proportion, and mix thoroughly to obtain a uniform
  • the mass ratios of solid electrolyte and binder are 80%-100% and 0%-20% respectively.
  • a binder is used in this invention, which affects the purity of the dispersion system, and the solid electrolyte slurry cannot be stored for a long time.
  • the existing technology cannot simultaneously meet the requirements of simple process, stable solid content, good redispersibility, and low cost. Moreover, there is a technical bias in the existing technology that low solid content dispersions are more stable.
  • a stable dispersion with a solid content in the range of 40wt%-85wt% is prepared without additives.
  • the particles of the inorganic oxide solid electrolyte dispersion do not agglomerate within the solid content range, and have high solid content stability and particle size stability, which can reduce storage, transportation, and use costs.
  • the dispersion uses less solvent and can effectively reduce the preparation cost of the dispersion.
  • the invention of the present invention is to provide an inorganic oxide solid electrolyte dispersion with stable solid content.
  • the inorganic oxide solid electrolyte dispersion consists of a granular inorganic oxide solid electrolyte and a solvent, without additives, and without the need for inorganic oxidation. No modifications can be made to the solid electrolyte particles.
  • the solvent in the dispersion liquid is an aprotic solvent with a polarity of 4 to 8.
  • the solid content of the dispersion is 40wt%-85wt%.
  • the inorganic oxide solid electrolyte can be NASICON type electrolyte, garnet type electrolyte, perovskite type electrolyte, anti-perovskite type electrolyte, LiSICON type electrolyte, Li 1-x1 Ti 1-x1 M1 x1 OPO 4 , Li 1 +x2 H 1-x2 At least one of Al(PO 4 )O 1-y M 2y , LiAlPO 4 F x3 (OH) 1-x3 and Na- ⁇ / ⁇ “-Al 2 O 3 , where M1 is selected from At least one of Nb, Ta and Sb, M is selected from at least one of F, Cl, Br and I, 0 ⁇ x1 ⁇ 0.7, 0 ⁇ x2 ⁇ 1, 0 ⁇ x3 ⁇ 1, 0 ⁇ y ⁇ 0.1 ;
  • the inorganic oxide solid electrolyte is preferably Li 1+x4+n Al x4 Ti 2x4 Si n (P 1-n/3 O 4 ) 3 , Li 1+x4+n Al x4 Ge 2x4 Si n (P 1-n /3 O 4 ) 3 , Na 1+x4 Al x4 Ti 2-x4 Si n (P 1-n/3 O 4 ) 3 , Na 1+x5 Zr 2 Si x5 P 3-x5 O 12 , Li 7-z1 La 3 Zr 2-z1 A2 z1 O 12 , Li 7+z2 La 3 Zr 2 - z2 Y z2 O 12 , Li 7-3z3 Ga z3 La 3 Zr 2 O 12 , Li 3x6 La 2 / 3 - x6 TiO 3 , Li 3 OCl, Na 3 OCl, Li 14 Zn(GeO 4 ) 4 , Li 1-x1 Ti 1-x1 M1 x1 OPO 4 , Li 1+x2 H
  • the particle size of the inorganic oxide solid electrolyte in the inorganic oxide solid electrolyte dispersion is 50-1000 nm.
  • the solvent includes at least one of N-methylpyrrolidone, N,N-dimethylformamide, dimethylacetamide, 1,3-dioxopentane, and dimethyl carbonate.
  • Another invention of the present invention is to crush the inorganic oxide solid electrolyte particles by grinding.
  • the solid electrolyte particles interact with each other to form a stable solid state.
  • the grinding method has a crushing function, and the grinding process is not only Dispersing the inorganic oxide solid electrolyte is a process that promotes the interaction between particles. This grinding process reduces the proportion of free solvent in the dispersion and increases the proportion of the inorganic oxide solid electrolyte combined with the solvent, thereby increasing the inorganic oxide solid electrolyte. diffusion difficulty to achieve the effect of improving the stability of solid content. Simple ultrasonic dispersion cannot achieve our results.
  • the grinding method includes at least one of vertical stirring mill grinding, drum ball mill grinding and sand mill grinding.
  • the change in solid content of the dispersion was less than 2%.
  • the particle size change rate of the inorganic oxide solid electrolyte particles is less than 5%.
  • Another invention point of the present invention is to provide a method for preparing an inorganic oxide solid electrolyte dispersion, which is characterized in that it consists of the following steps:
  • the grinding time is 30 minutes to 15 hours;
  • the grinding linear speed is ⁇ 3m/s.
  • the application of the inorganic oxide solid electrolyte dispersion in batteries of the present invention includes application in at least one of liquid batteries, hybrid solid-liquid batteries and solid-state batteries.
  • the application methods of the inorganic oxide solid electrolyte dispersion in batteries include direct application or dilution to positive electrode plate blending, positive electrode plate surface coating, At least one of positive electrode particle surface coating and separator coating can improve the safety performance, rate performance and cycle performance of the battery.
  • the present invention prepares a solid content stable dispersion with a solid content in the range of 40wt%-85wt% without additives, and improves solid content stability and particle size stability by increasing particle surface repulsion and delaying the settling speed of inorganic particles.
  • the present invention has the following advantages and outstanding effects:
  • the use of the additive-free inorganic oxide solid electrolyte dispersion with stable solid content of the present invention can solve the problem that the dispersion cannot be used due to electrolyte sedimentation during transportation, storage, and feeding.
  • the matching of the system, preparation method and reasonable solid content range are the key technical points.
  • the solution has the advantages of simple process, low cost, stable solid content and particle size during long-term storage, uniform upper and lower layers of the dispersion, good redispersibility, no need for additives, no need for solid electrolyte surface pretreatment, and no need to adjust PH.
  • the battery using the dispersion of the present invention has better consistency and higher battery assembly efficiency.
  • the inorganic oxide solid electrolyte dispersion in the present invention is a nano dispersion with high solid content. Compared with the low solid content dispersion in the prior art, the transportation cost is reduced due to the reduction of solvents, the risk is reduced, and the solid content is stable. It has good properties and particle size stability, and the solid electrolyte does not settle. During storage, because less solvent is used, storage costs are reduced, solid content stability and particle size stability are good, and the solid electrolyte does not settle. During use, the required amount of solid electrolyte dispersion can be accurately added to the slurry as needed, and the upper and lower layers of the dispersion will be uniform. Therefore, the present invention has significant economic benefits and practical effects.
  • the present invention does not require the use of additives to maintain dispersion stability, can reduce costs and improve quality. system purity to reduce the impact on practical applications.
  • the present invention reduces the amount of solvent and reduces the cost of dispersion preparation.
  • the present invention does not require pretreatment on the surface of ceramic particles.
  • the preparation method of the present invention is simple, scalable, and compatible with existing grinding processes.
  • the solid content stability testing steps are as follows:
  • Step 1 Add 500 parts by weight of zirconium balls, 100 parts by weight of Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 powder with a particle size of 3 ⁇ m and 67 parts by weight of NMP into the grinding cavity, and stir evenly;
  • Step 2 Use a roller ball mill to grind the zirconium balls, Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 powder and NMP mixed in the grinding chamber into a dispersion slurry with a solid content of 60wt% and D50: 306nm.
  • the grinding time is 12 hours, and the grinding linear speed is 6m/s.
  • the prepared dispersion was subjected to dispersion solid content stability test and dispersion particle size stability test. The results are shown in Table 1 and Table 2.
  • Step 1 Add 500 parts by weight of zirconium balls, 100 parts by weight of Li 7 La 3 Zr 2 O 12 powder with a particle size of 3 ⁇ m, and 67 parts by weight of NMP into the grinding cavity, and stir evenly;
  • the prepared dispersion was subjected to dispersion solid content stability test and dispersion particle size stability test. The results are shown in Table 1 and Table 2.
  • Step 1 Add 500 parts by weight of zirconium balls, 100 parts by weight of Li 0.35 La 0.55 TiO 3 powder with a particle size of 3 ⁇ m and 43 parts by weight of DMF into the grinding cavity, and stir evenly;
  • the prepared dispersion was subjected to dispersion solid content stability test and dispersion particle size stability test. The results are shown in Table 1 and Table 2.
  • Step 1 Add 500 parts by weight of zirconium balls, 100 parts by weight of LiHAl(PO 4 )O 0.95 F 0.1 powder with a particle size of 3 ⁇ m and 67 parts by weight of DMF into the grinding cavity, and stir evenly;
  • Step 2 Use a ball mill to grind the zirconium balls, LiHAl(PO 4 )O 0.95 F 0.1 powder and DMF mixed in the grinding chamber into a dispersion slurry with a solid content of 60wt% and D50: 203nm.
  • the prepared dispersion was subjected to dispersion solid content stability test and dispersion particle size stability test. The results are shown in Table 1 and Table 2.
  • Step 1 Add 500 parts by weight of zirconium balls, 100 parts by weight of Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 powder with a particle size of 4 ⁇ m and 150 parts by weight of NMP into the grinding cavity, and stir evenly;
  • the prepared dispersion was subjected to dispersion solid content stability test and dispersion particle size stability test. The results are shown in Table 1 and Table 2.
  • Step 1 Add 500 parts by weight of zirconium balls, 100 parts by weight of Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 powder with a particle size of 5 ⁇ m and 100 parts by weight of NMP into the grinding cavity, and stir evenly;
  • Step 2 Use a ball mill to grind the zirconium balls, Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 powder and NMP mixed in the grinding chamber until the solid content is 50wt%.
  • the prepared dispersion was subjected to dispersion solid content stability test and dispersion particle size stability test. The results are shown in Table 1 and Table 2.
  • Step 1 Add 500 parts by weight of zirconium balls, 100 parts by weight of Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 powder with a particle size of 6 ⁇ m and 18 parts by weight of NMP into the grinding cavity, and stir evenly;
  • the prepared dispersion was subjected to dispersion solid content stability test and dispersion particle size stability test. The results are shown in Table 1 and Table 2.
  • Step 1 Add 100 parts by weight of zirconium balls, 100 parts by weight of Li 7 La 3 Zr 2 O 12 powder with a particle size of 3 ⁇ m and 67 parts by weight of DMAc into the grinding cavity, and stir evenly;
  • the prepared dispersion was subjected to dispersion solid content stability test and dispersion particle size stability test. The results are shown in Table 1 and Table 2.
  • Step 1 Add 100 parts by weight of zirconium balls, 100 parts by weight of Li 7 La 3 Zr 2 O 12 powder with a particle size of 3 ⁇ m and 67 parts by weight of DMAc into the grinding cavity, and stir evenly;
  • the prepared dispersion was subjected to dispersion solid content stability test and dispersion particle size stability test. The results are shown in Table 1 and Table 2.
  • Step 1 Add 500 parts by weight of zirconium balls, 100 parts by weight of Li 7 La 3 Zr 2 O 12 powder with a particle size of 3 ⁇ m and 67 parts by weight of DMAc into the grinding cavity, and stir evenly;
  • the prepared dispersion was subjected to dispersion solid content stability test and dispersion particle size stability test. The results are shown in Table 1 and Table 2.
  • Step 1 Add 2000 parts by weight of zirconium balls, 100 parts by weight of Li 7 La 3 Zr 2 O 12 powder with a particle size of 1 ⁇ m and 150 parts by weight of DMAc into the grinding cavity, and stir evenly;
  • Step 2 Use a sand mill to mix the zirconium balls and Li 7 La 3 Zr 2 O 12 in the grinding chamber.
  • the powder and DMAc were ground to form a dispersion slurry with a solid content of 40wt% and D50: 50nm.
  • the grinding time was 24 hours and the grinding linear speed was 8m/s.
  • the prepared dispersion was subjected to dispersion solid content stability test and dispersion particle size stability test. The results are shown in Table 1 and Table 2.
  • Step 1 Add 500 parts by weight of zirconium balls, 100 parts by weight of Li 0.35 La 0.55 TiO 3 powder with a particle size of 3 ⁇ m, 2 parts by weight of PVDF and 122 parts by weight of NMP into the grinding cavity, and stir evenly;
  • Step 2 Use a ball mill to grind the zirconium balls, Li 0.35 La 0.55 TiO 3 powder and NMP mixed in the grinding chamber into a dispersion slurry with a solid content of 45wt% and D50: 603nm.
  • the prepared dispersion was subjected to dispersion solid content stability test and dispersion particle size stability test. The results are shown in Table 1 and Table 2.
  • Step 1 Add 500 parts by weight of zirconium balls, 100 parts by weight of Li 0.35 La 0.55 TiO 3 powder with a particle size of 3 ⁇ m, 3 parts by weight of acrylate and 150 parts by weight of NMP into the grinding cavity, and stir evenly;
  • Step 2 Use a ball mill to grind the zirconium balls, Li 0.35 La 0.55 TiO 3 powder and NMP mixed in the grinding chamber into a dispersion slurry with a solid content of 40wt% and D50: 299nm.
  • the prepared dispersion was subjected to dispersion solid content stability test and dispersion particle size stability test. The results are shown in Table 1 and Table 2.
  • Step 1 Put 100 parts by weight of LiHAl(PO 4 )O 0.95 F 0.1 powder with a particle size of 300 nm and 233 parts by weight of NMP into a container and seal it. Add the container to the ultrasonic pool for ultrasonic for 15 hours, with a solid content of 30wt%;
  • the prepared dispersion was subjected to dispersion solid content stability test and dispersion particle size stability test. The results are shown in Table 1 and Table 2.
  • Step 1 Add 500 parts by weight of zirconium balls, 100 parts by weight of Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 powder with a particle size of 3 ⁇ m and 900 parts by weight of NMP into the grinding cavity, and stir evenly;
  • the prepared dispersion was subjected to dispersion solid content stability test and dispersion particle size stability test. The results are shown in Table 1 and Table 2.
  • the dispersion of the present invention has excellent solid content stability and particle size stability, wherein the solid content stability is ⁇ 2% and the particle size stability is ⁇ 5%. It can be seen from Examples 1, 5, and 6 that as the solid content increases, the solid content stability and particle size stability increase. It can be seen from Examples 8-10 that as the electrolyte particle size decreases, the solid content stability and particle size stability increase. In Comparative Examples 1 and 2, due to the addition of thickener, the viscosity of the dispersion increased to 15000mP ⁇ s and 13000mP ⁇ s, but because the thickener had little effect on the free solvent ratio, the solid content stability and particle size stability were far away. Far worse than the dispersion of the present invention.
  • the prepared dispersion can be mixed and used in the positive electrode, or coated on the surface of the positive electrode sheet, or coated on the surface of the positive electrode material, which can improve the electrical performance and safety performance of the battery.

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Abstract

本发明公开了一种电池用固含量稳定的无机氧化物固态电解质分散液及其制备方法和应用。本发明的无机氧化物固态电解质分散液由颗粒状无机氧化物固态电解质和溶剂组成，无添加剂，该分散液中溶剂为极性4-8的非质子溶剂；该分散液固含量在40wt％-85wt％。本发明所述的无机氧化物固态电解质分散液在该固含量范围内颗粒不发生团聚，稳定性高，可降低存储、运输和使用的成本。由于固含量较高，该分散液使用了更少的溶剂，可以有效降低分散液的制备成本。

Description

一种电池用固含量稳定的无机氧化物固态电解质分散液及其制备方法和应用
相关申请的交叉引用
本申请要求2022年04月13日提交的中国专利申请202210385392.2的权益，该申请的内容通过引用被合并于本文。
技术领域
本发明涉及锂电池技术领域，尤其涉及一种电池用固含量稳定的无机氧化物固态电解质分散液及其制备方法和应用。
背景技术
随电池能量密度不断提高，随之而来的安全问题变得更加显著。在电池中引入可取代易燃有机电解液的无机固态电解质，尤其是无机氧化物固态电解质，通常包括应用于极片改性和隔膜改性，可以提高电池安全性能。实际应用中，需要先将无机氧化物固态电解质制备成纳米分散液使用。但是，实际应用中分散液运输、存储、和上料使用过程中，由于重力作用和颗粒间的相互作用，无机氧化物固态电解质容易沉降在容器底部，导致分散液上下层固含量不均，物料在运输中和管路中存放的时间大于24小时，固含量不稳定直接造成上料时上料值不准确，给生产造成困难，严重时甚至发生固体沉降在容器底部并结块的现象，使材料无法重新分散均匀甚至不能使用。此外，固含 不稳定常伴随粒度不稳定，而分散液粒度稳定性差则容易造成使用时效果不佳。尤其对于大规模生产，需要储备库存，存放时间在三十天以上，长时间存放对分散液稳定性要求更高。为提高固含量稳定性和固态电解质粒度稳定性，此时所用分散液固含量通常小于10wt％，因为现有技术一般认为低固含量有助于提高分散液固含量稳定性和粒度稳定性。而且现在的使用方式是现配现用，这严重影响了实际规模化生产的效率。上述问题严重阻碍了无机氧化物固态电解质的大规模应用。为了使用无机氧化物固态电解质，通常需要无机氧化物固态电解质分散液在运输、存储、和上料使用过程中固含量变化量＜2％。现有技术中的无机氧化物固态电解质纳米分散液的固含量较低，通常小于30wt％，甚至小于10wt％。然而运输时，溶剂含量越多，运输成本越高，且如果使用易燃易爆有机溶剂则危险性越高，因此低固含量分散液普遍运输成本高且危险性高。存储时如果使用固含量很低的分散液则需要大量溶剂，增加存储成本。使用时，也可能由于固含量过低无法配合现有电极材料浆料配方使用。因此，在保证一定固含量的前提下提高无机氧化物固态电解质纳米分散液的固含量稳定性很重要。
目前提高分散液固含量稳定性，防止沉降的方法主要包括添加分散剂、离心处理、制备特殊形貌材料的方法。
CN112876901A公开了一种水分散性功能陶瓷墨水，是将Li7La3Zr2O12粉体混合物分散在聚丙烯酰胺水溶液分散介质中得到的，黏度3～5mPa·s、表面张力55～65mN/m，陶瓷墨水具有优异的稳定 性，每100mL分散介质中分散有6～15g的Li7La3Zr2O12粉体混合物。该发明中由于固含量过低，存在上述低固含分散液在运输、存储、和使用时的问题。
CN102760510B公开了一种不使用任何助剂制造出纯度高、固体含量高、透明度好、导电性优良、稳定存储、不凝聚、不沉降的ATO纳米晶水系分散液。该方法在通过砂磨机研磨，并超声破碎分散制备得到普通ATO水系分散液后，将该分散液经过高速离心，得到粒度小的上清液。该方法认为低固含量下可以提高分散液的稳定性。方法的优点在于不使用任何助剂，通过离心的方法加速大颗粒的沉降，离心不沉降的上清液小颗粒在普通条件下静置稳定，不容易沉降。缺点在于经过离心后的上清液固含量降低，且离心后的下层固体易结块，需要重新经过多级破碎得到分散液，工艺复杂，整个过程效率低。而且该方法制备的分散液固含量低。
CN201810560205.3公开了一种使用分散剂结合低温离心技术制备固含量稳定的Zn2TiO4分散液的方法。该方法在离心过程中出现固含量梯度分布的现象，浆料整体固含量均一性差。需要注意的是就算使用分散剂，分散液的固含量稳定性也难以完全保证，调整体系稳定性的过程往往需要精确的体系内各参数的匹配。只加分散剂无法达到长期存储的效果。
CN113964450A提供一种电池隔膜涂布液及其制备方法，所述电池隔膜涂布液中包含陶瓷纳米线，直径为1～1000nm，长度为0.05～100μm。然而，纳米线分散液的均匀分散除了需要纳米线与纳米线之 间的氢键作用，还需要配合使用其他助剂和陶瓷颗粒，配方复杂。
CN202010494930.2涉及一种高机械强度的固态电解质薄膜的制备方法，其制备方法包括以下步骤：制备固态电解质浆料，将固态电解质，粘结剂，按比例加入到分散液中，充分混合得到均匀分散的电解质浆料，固态电解质与粘结剂的质量比分别为80％-100％与0％-20％。然而该发明中使用了粘结剂，影响了分散液体系纯度，且固态电解质浆料不能长时间存储。
总的来说，现有技术无法同时满足工艺简单、固含量稳定、再分散性好、成本低的要求。而且，现有技术存在低固含量分散液更稳定的技术偏见。
发明内容
针对以上技术存在的局限性，在本专利中，在无添加剂的条件下制备固含量在40wt％-85wt％范围的固含量稳定分散液。所述的无机氧化物固态电解质分散液在所述固含量范围内颗粒不发生团聚，固含量稳定性和粒度稳定性高，可降低存储、运输、和使用时的成本。该分散液使用的溶剂更少，可以有效降低分散液的制备成本。
本发明的发明点是提供一种固含量稳定的无机氧化物固态电解质分散液，所述无机氧化物固态电解质分散液由颗粒状无机氧化物固态电解质和溶剂组成，无添加剂，且无需对无机氧化物固态电解质颗粒做任何修饰。
所述分散液中溶剂为极性4～8的非质子溶剂。
所述分散液的固含量为40wt％-85wt％。
所述无机氧化物固态电解质可以是NASICON型电解质、石榴石型电解质、钙钛矿型电解质、反钙钛矿型电解质、LiSICON型电解质、Li1-x1Ti1-x1M1x1OPO4、Li1+x2H1-x2Al(PO4)O1-yM2y、LiAlPO4Fx3(OH)1-x3和Na-β/β“-Al2O3中的至少一种，其中M1选自Nb、Ta和Sb中的至少一种，M选自F、Cl、Br和I中的至少一种，0≤x1≤0.7，0≤x2＜1，0≤x3＜1，0＜y＜0.1；
所述无机氧化物固态电解质优选为Li1+x4+nAlx4Ti2x4Sin(P1-n/3O4)3、Li1+x4+nAlx4Ge2x4Sin(P1-n/3O4)3、Na1+x4Alx4Ti2-x4Sin(P1-n/3O4)3、Na1+x5Zr2Six5P3-x5O12、Li7-z1La3Zr2-z1A2z1O12、Li7+z2La3Zr2-z2Yz2O12、Li7-3z3Gaz3La3Zr2O12、Li3x6La2/3-x6TiO3、Li3OCl、Na3OCl、Li14Zn(GeO4)4、Li1-x1Ti1-x1M1x1OPO4、Li1+x2H1-x2Al(PO4)O1-yM2y、LiAlPO4Fx3(OH)1-x3和Na-β/β“-Al2O3中的至少一种，其中M1选自Nb、Ta和Sb中的至少一种，M选自F、Cl、Br和I中的至少一种，A2选自Nb、Ta和W中的至少一种，0≤x1≤0.7，0≤x2＜1，0≤x3＜1，0＜x4＜0.6，0≤x5≤3，0＜x6＜0.16，0＜y＜0.1，0≤z1≤1，0≤z2≤1，0≤z3≤0.3，0≤n＜3。
所述无机氧化物固态电解质分散液中无机氧化物固态电解质的颗粒大小为50-1000nm。
优选的，所述溶剂的种类包括N-甲基吡咯烷酮、N，N-二甲基甲酰胺、二甲基乙酰胺、1，3-二氧戊烷、碳酸二甲酯中的至少一种。
本发明的另一个发明点为，采用研磨的方式破碎无机氧化物固态电解质颗粒，在所述固含量范围内，固态电解质颗粒间相互作用后形成固含量稳定状态。所述研磨方式具有破碎功能，研磨过程不仅仅是 对无机氧化物固态电解质做分散，更是促进颗粒间相互作用的过程，这个研磨过程降低了分散液中自由溶剂的比例，提高无机氧化物固态电解质结合溶剂的比例，从而增加无机氧化物固态电解质的扩散难度，达到提高固含量稳定性的效果。简单的超声分散达不到我们的效果。
所述研磨方式包括立式搅拌磨研磨、滚筒球磨机研磨和砂磨机研磨的至少一种。
所述分散液在静置30天后，分散液的固含量的变化值小于2％。
所述分散液在静置30天后，无机氧化物固态电解质颗粒的粒度变化率小于5％。
本发明的另一个发明点为，提供一种无机氧化物固态电解质分散液的制备方法，其特征在于，由以下步骤组成：
(1)混合：将研磨介质、颗粒状无机氧化物固态电解质和溶剂加入研磨腔体，所述研磨介质、无机氧化物固态电解质和溶剂的质量比为(2000-100)∶100∶(17-150)；
(2)研磨：将在研磨腔中混合好的研磨介质、无机氧化物固态电解质和溶剂进行研磨，得到固含量稳定的分散液浆料。
优选的，所述的研磨时间为30分钟-15小时；
优选的，所述的研磨线速度≥3m/s。
本发明所述无机氧化物固态电解质分散液在电池中的应用，包括应用于液态电池、混合固液电池和固态电池中的至少一种。
具体的，所述无机氧化物固态电解质分散液在电池中的应用方式包括直接应用于或经稀释后应用于正极极片掺混、正极极片表面涂覆、 正极颗粒表面包覆和隔膜涂覆中的至少一种，可提高电池的安全性能、倍率性能和循环性能。
本发明在无添加剂的条件下制备固含量在40wt％-85wt％范围的固含量稳定分散液，通过增加颗粒表面斥力，延缓无机颗粒沉降速度来提高固含量稳定性和粒度稳定性。
本发明相比现有技术，具有如下优点及突出性效果：
使用本发明所述的固含量稳定的无添加剂的无机氧化物固态电解质分散液可以解决分散液运输、存储、和上料使用过程中存在的由于电解质沉降而无法使用的问题。其中体系的匹配、制备方法和合理的固含量范围是技术关键点。所述方案具有工艺简单、成本低、长时间存储固含量稳定且粒度稳定、分散液上下层均一、再分散性好、无需添加剂、无需固态电解质表面预处理、无需调整PH等优势。对比使用其他分散液，使用本发明中分散液的电池一致性好，电池成组效率高。
本发明中无机氧化物固态电解质分散液为纳米分散液，固含量高，对比现有技术中的低固含量的分散液，由于溶剂减少，运输成本降低，且危险性减小，且固含量稳定性和粒度稳定性好，固态电解质不沉降。存储时，因为使用溶剂量少，减少了存储成本，且固含量稳定性和粒度稳定性好，固态电解质不沉降。使用时，可以根据需要在浆料中准确加入所需用量的固态电解质分散液，分散液上下层均一。因此，本发明经济效益和使用效果显著。
本发明无需使用添加剂保持分散稳定性，可降低成本，并提高体 系纯度，减小实际应用时的影响。
本发明提高固含量后，减少了溶剂的用量，降低了分散液制备的成本。
本发明无需对陶瓷颗粒表面做预处理。
本发明该制备方法简单可放大，与现有研磨工艺兼容。
具体实施方式
下面结合具体实施例对本发明进行具体的描述，有必要在此指出的是以下实施例只用于对本发明的进一步说明，不能理解为对本发明保护范围的限制，本领域技术人员根据本发明内容对本发明做出的一些非本质的改进和调整仍属本发明的保护范围。
分散液固含量稳定性测试方法：
使用烘干法测试分散液的固含量，固含量稳定性测试步骤如下：
(1)取制备好的分散液测试固含量，记录为初始固含量。
(2)取100mL分散液于150mL实验瓶中，将实验瓶密封静置30天。30天后取实验瓶中距离液面5mm处1mL分散液，测试固含量，记为分散液上层固含量值w1。取实验瓶中距离瓶底5mm处1mL分散液，测试固含量，记为分散液下层固含量值w2。
(3)利用上下层固含量值w1与w2与初始固含量值w0偏差衡量分散液固含量稳定性S。其中，上层固含量变化值为S1＝|w1-w0|/w0×100％，下层固含量变化值为 S2＝|w2-w0|/w0×100％；S1和S2的值越小，表明浆料越稳定。
分散液粒度稳定性测试方法：
使用纳米粒度仪测试分散液的粒度，所用溶剂与分散剂溶剂一致，粒度稳定性测试步骤如下：
(1)取制备好的分散液测试粒度，记录为初始平均粒度D0。
(2)取100mL分散液于150mL实验瓶中，将实验瓶密封静置30天。30天后取实验瓶中距离液面5mm处1mL分散液，测试粒度，记为分散液上层粒度值D1。取实验瓶中距离瓶底5mm处1mL分散液，测试粒度，记为分散液下层粒度值D2。
(4)利用上下层粒度值D1与D2与初始粒度值D0偏差衡量分散液粒度稳定性T。其中，浆料上层颗粒粒度变化值为T1＝|D1-D0|/D0×100％，下层固含量变化值为T2＝|D2-D0|/D0×100％；T1和T2的值越小，表明分散液粒度越稳定。
实施例示例1：
步骤一：将500重量份锆球、粒径3μm的100重量份Li1.4Al0.4Ti1.6(PO4)3粉末和67重量份NMP加入研磨腔体，搅拌均匀；
步骤二：使用滚筒球磨机将在研磨腔中混合好的锆球、Li1.4Al0.4Ti1.6(PO4)3粉末和NMP进行研磨，研磨成固含量60wt％，D50：306nm的分散液浆料，研磨时间为12小时，研磨线速度＝6m/s。
所制备的分散液进行分散液固含量稳定性测试和分散液粒度稳定性测试，结果见表1和表2。
实施例示例2：
步骤一：将500重量份锆球、粒径3μm的100重量份Li7La3Zr2O12粉末和67重量份NMP加入研磨腔体，搅拌均匀；
步骤二：使用砂磨机将在研磨腔中混合好的锆球、Li7La3Zr2O12粉末和NMP进行研磨，研磨成固含量60wt％，D50：301nm的分散液浆料，研磨时间为6小时，研磨线速度＝8m/s。
所制备的分散液进行分散液固含量稳定性测试和分散液粒度稳定性测试，结果见表1和表2。
实施例示例3：
步骤一：将500重量份锆球、粒径3μm的100重量份Li0.35La0.55TiO3粉末和43重量份DMF加入研磨腔体，搅拌均匀；
步骤二：使用立式搅拌磨将在研磨腔中混合好的锆球、Li0.35La0.55TiO3粉末和DMF进行研磨，研磨成固含量70wt％，D50：402nm的分散液浆料，研磨时间为12小时，研磨线速度＝7m/s。
所制备的分散液进行分散液固含量稳定性测试和分散液粒度稳定性测试，结果见表1和表2。
实施例示例4：
步骤一：将500重量份锆球、粒径3μm的100重量份LiHAl(PO4)O0.95F0.1粉末和67重量份DMF加入研磨腔体，搅拌均匀；
步骤二：使用球磨机将在研磨腔中混合好的锆球、LiHAl(PO4)O0.95F0.1粉末和DMF进行研磨，研磨成固含量60wt％，D50：203nm的分散液浆料，研磨时间为12小时，研磨线速度＝6m/s。
所制备的分散液进行分散液固含量稳定性测试和分散液粒度稳定性测试，结果见表1和表2。
实施例示例5：
步骤一：将500重量份锆球、粒径4μm的100重量份Li1.4Al0.4Ti1.6(PO4)3粉末和150重量份NMP加入研磨腔体，搅拌均匀；
步骤二：使用球磨机将在研磨腔中混合好的锆球、Li1.4Al0.4Ti1.6(PO4)3粉末和NMP进行研磨，研磨成固含量40wt％，D50：307nm的分散液浆料，研磨时间为12小时，研磨线速度＝5m/s。
所制备的分散液进行分散液固含量稳定性测试和分散液粒度稳定性测试，结果见表1和表2。
实施例示例6：
步骤一：将500重量份锆球、粒径5μm的100重量份Li1.4Al0.4Ti1.6(PO4)3粉末和100重量份NMP加入研磨腔体，搅拌均匀；
步骤二：使用球磨机将在研磨腔中混合好的锆球、Li1.4Al0.4Ti1.6(PO4)3粉末和NMP进行研磨，研磨成固含量50wt％， D50：300nm的分散液浆料，研磨时间为14小时，研磨线速度＝7m/s。
所制备的分散液进行分散液固含量稳定性测试和分散液粒度稳定性测试，结果见表1和表2。
实施例示例7：
步骤一：将500重量份锆球、粒径6μm的100重量份Li1.4Al0.4Ti1.6(PO4)3粉末和18重量份NMP加入研磨腔体，搅拌均匀；
步骤二：使用球磨机将在研磨腔中混合好的锆球、Li1.4Al0.4Ti1.6(PO4)3粉末和NMP进行研磨，研磨成固含量85wt％，D50：811nm的分散液浆料，研磨时间为8小时，研磨线速度＝6m/s。
所制备的分散液进行分散液固含量稳定性测试和分散液粒度稳定性测试，结果见表1和表2。
实施例示例8：
步骤一：将100重量份锆球、粒径3μm的100重量份Li7La3Zr2O12粉末和67重量份DMAc加入研磨腔体，搅拌均匀；
步骤二：使用立式搅拌磨将在研磨腔中混合好的锆球、Li7La3Zr2O12粉末和DMAc进行研磨，研磨成固含量60wt％，D50：1001nm的分散液浆料，研磨时间为6小时，研磨线速度＝4m/s。
所制备的分散液进行分散液固含量稳定性测试和分散液粒度稳定性测试，结果见表1和表2。
实施例示例9：
步骤一：将100重量份锆球、粒径3μm的100重量份Li7La3Zr2O12粉末和67重量份DMAc加入研磨腔体，搅拌均匀；
步骤二：使用立式搅拌磨将在研磨腔中混合好的锆球、Li7La3Zr2O12粉末和DMAc进行研磨，研磨成固含量60wt％，D50：799nm的分散液浆料，研磨时间为8小时，研磨线速度＝4m/s。
所制备的分散液进行分散液固含量稳定性测试和分散液粒度稳定性测试，结果见表1和表2。
实施例示例10：
步骤一：将500重量份锆球、粒径3μm的100重量份Li7La3Zr2O12粉末和67重量份DMAc加入研磨腔体，搅拌均匀；
步骤二：使用砂磨机将在研磨腔中混合好的锆球、Li7La3Zr2O12粉末和DMAc进行研磨，研磨成固含量60wt％，D50：500nm的分散液浆料，研磨时间为6小时，研磨线速度＝7m/s。
所制备的分散液进行分散液固含量稳定性测试和分散液粒度稳定性测试，结果见表1和表2。
实施例示例11：
步骤一：将2000重量份锆球、粒径1μm的100重量份Li7La3Zr2O12粉末和150重量份DMAc加入研磨腔体，搅拌均匀；
步骤二：使用砂磨机将在研磨腔中混合好的锆球、Li7La3Zr2O12 粉末和DMAc进行研磨，研磨成固含量40wt％，D50：50nm的分散液浆料，研磨时间为24小时，研磨线速度＝8m/s。
所制备的分散液进行分散液固含量稳定性测试和分散液粒度稳定性测试，结果见表1和表2。
对比例示例1：
步骤一：将500重量份锆球、粒径3μm的100重量份Li0.35La0.55TiO3粉末、2重量份的PVDF和122重量份NMP加入研磨腔体，搅拌均匀；
步骤二：使用球磨机将在研磨腔中混合好的锆球、Li0.35La0.55TiO3粉末和NMP进行研磨，研磨成固含量45wt％，D50：603nm的分散液浆料，研磨时间为8小时，研磨线速度＝6m/s；
所制备的分散液进行分散液固含量稳定性测试和分散液粒度稳定性测试，结果见表1和表2。
对比例示例2：
步骤一：将500重量份锆球、粒径3μm的100重量份Li0.35La0.55TiO3粉末、3重量份的丙烯酸酯和150重量份NMP加入研磨腔体，搅拌均匀；
步骤二：使用球磨机将在研磨腔中混合好的锆球、Li0.35La0.55TiO3粉末和NMP进行研磨，研磨成固含量40wt％，D50：299nm的分散液浆料，研磨时间为10小时，研磨线速度＝5m/s；
所制备的分散液进行分散液固含量稳定性测试和分散液粒度稳定性测试，结果见表1和表2。
对比例示例3：
步骤一：将粒径300nm的100重量份LiHAl(PO4)O0.95F0.1粉末和233重量份NMP装入容器并密封，将容器加入超声池进行超声15小时，固含量30wt％；
所制备的分散液进行分散液固含量稳定性测试和分散液粒度稳定性测试，结果见表1和表2。
对比例示例4：
步骤一：将500重量份锆球、粒径3μm的100重量份Li1.4Al0.4Ti1.6(PO4)3粉末和900重量份NMP加入研磨腔体，搅拌均匀；
步骤二：使用球磨机将在研磨腔中混合好的锆球、Li1.4Al0.4Ti1.6(PO4)3粉末和NMP进行研磨，研磨成固含量10wt％，D50：300nm的分散液浆料，研磨时间为12小时，研磨线速度＝6m/s；
所制备的分散液进行分散液固含量稳定性测试和分散液粒度稳定性测试，结果见表1和表2。
表1.分散液固含量稳定性测试结果

表2.分散液粒度稳定性测试结果

通过实施例可以看出，本发明所述分散液具有优异的固含量稳定性和粒度稳定性，其中固含量稳定性＜2％，粒度稳定性＜5％。从实施例1、5、6可知，随固含量提高，固含量稳定性和粒度稳定性提高。从实施例8-10可知，随电解质颗粒粒度减小，固含量稳定性和粒度稳定性提高。在对比例1和2中，由于添加了增稠剂，分散液粘度升高到15000mP·s和13000mP·s，但因为增稠剂对自由溶剂比例影响小所以固含量稳定性和粒度稳定性远远差于本发明所述分散液。从对比例3可知，本发明所述研磨工艺优于超声工艺，研磨过程是不可替代的，超声工艺得到的分散液固含量稳定性和粒度稳定性较差。最后，从对比例4可知，当固含量较低时，分散液的固含量稳定性和粒度稳定性较差。
制备好的分散液掺混在正极中使用，或者涂覆在正极极片表面使用，或者包覆在正极材料表面使用，都可以提高电池的电性能和安全性能。
可以理解的是，以上实施方式仅仅是为了说明本发明的原理而采用的示例性实施方式，然而本发明并不局限于此。对于本领域内的普通技术人员而言，在不脱离本发明的精神和实质的情况下，可以做出各种变型和改进，这些变型和改进也视为本发明的保护范围。

Claims (9)

  1. 一种电池用固含量稳定的无机氧化物固态电解质分散液，其特征在于，
    所述无机氧化物固态电解质分散液由颗粒状无机氧化物固态电解质和溶剂组成，无添加剂；
    所述无机氧化物固态电解质分散液中溶剂为极性4～8的非质子溶剂；
    所述无机氧化物固态电解质分散液的固含量为40wt％-85wt％。
  2. 根据权利要求1所述的无机氧化物固态电解质分散液，其中，
    所述无机氧化物固态电解质选自NASICON型电解质、石榴石型电解质、钙钛矿型电解质、反钙钛矿型电解质、LiSICON型电解质、Li1-x1Ti1-x1M1x1OPO4、Li1+x2H1-x2Al(PO4)O1-yM2y、LiAlPO4Fx3(OH)1-x3和Na-β/β″-Al2O3中的至少一种，其中M1选自Nb、Ta和Sb中的至少一种，M选自F、Cl、Br和I中的至少一种，0≤x1≤0.7，0≤x2<1，0≤x3<1，0<y<0.1；
    所述无机氧化物固态电解质分散液中无机氧化物固态电解质的颗粒大小为50-1000nm；
    所述溶剂包括N-甲基吡咯烷酮、N,N-二甲基甲酰胺、二甲基乙酰胺、1,3-二氧戊烷和碳酸二甲酯中的至少一种；
    所述固含量为50wt％-80wt％。
  3. 根据权利要求2所述的无机氧化物固态电解质分散液，其中，所述固含量为55wt％-wt75％。
  4. 根据权利要求1所述的无机氧化物固态电解质分散液，其中，
    所述无机氧化物固态电解质选自Li1+x4+nAlx4Ti2x4Sin(P1-n/3O4)3、Li1+x4+nAlx4Ge2 x4Sin(P1-n/3O4)3、Na1+x4Alx4Ti2-x4Sin(P1-n/3O4)3、Na1+x5Zr2Six5P3-x5O12、Li7-z1La3Zr2-z1A2z1O12、Li7+z2La3Zr2-z2Yz2O12、Li7-3z3Gaz3La3Zr2O12、Li3x6La2/3-x6TiO3、Li3OCl、Na3OCl、Li14Zn(GeO4)4、Li1-x1Ti1-x1M1x1OPO4、Li1+x2H1-x2Al(PO4)O1-yM2y、LiAlPO4Fx3(OH)1-x3和Na-β/β″-Al2O3中的至少一种，其中M1选自Nb、Ta和Sb中的至少一种，M选自F、Cl、Br和I中的至少一种，A2选自Nb、Ta和W中的至少一种，0≤x1≤0.7，0≤x2<1，0≤x3<1，0<x4<0.6，0≤x5≤3，0<x6<0.16，0<y<0.1，0≤z1≤1，0≤z2≤1，0≤z3≤0.3，0≤n<3。
  5. 根据权利要求1所述的无机氧化物固态电解质分散液，其中，所述无机氧化物固态电解质分散液静置30天后，所述无机氧化物固态电解质分散液的固含量变化值小于2％。
  6. 一种权利要求1所述的无机氧化物固态电解质分散液的制备方法，其特征在于，所述制备方法包括：采用研磨的方式破碎颗粒状无机氧化物固态电解质，破碎后的颗粒间相互作用后形成固含量稳定状态。
  7. 根据权利要求6所述的制备方法，其中，所述制备方法具体包括以下步骤：
    (1)混合：将研磨介质、颗粒状无机氧化物固态电解质和溶剂加入研磨腔体，所述研磨介质、无机氧化物固态电解质和溶剂的质量比为(2000-100):100:(17-150)；
    (2)研磨：将在研磨腔中混合好的研磨介质、无机氧化物固态电解质和溶剂进行研磨，得到固含量稳定的分散液浆料。
  8. 一种权利要求1-5中任意一项所述的无机氧化物固态电解质分散液在电池中的应用，其特征在于，所述应用包括应用于液态电池、混合固液电池和固态电池中的至少一种。
  9. 根据权利要求8所述的应用，其中，所述应用包括直接应用于或经稀释后应用于正极极片掺混、正极极片表面涂覆、正极颗粒表面包覆和隔膜涂覆中的至少一种。
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109301314A (zh) * 2017-07-24 2019-02-01 微宏动力系统（湖州）有限公司 一种无机固体电解质复合浆料的制备方法及无机固体电解质复合浆料
CN109478685A (zh) * 2016-06-03 2019-03-15 富士胶片株式会社 固体电解质组合物、以及含固体电解质的片材、全固态二次电池、电极片及它们的制造方法
CN113841278A (zh) * 2019-05-31 2021-12-24 日本瑞翁株式会社 全固态二次电池用浆料组合物、含固态电解质层及全固态二次电池、以及全固态二次电池用浆料组合物的制造方法
WO2022004884A1 (ja) * 2020-07-02 2022-01-06 富士フイルム株式会社 全固体二次電池用シート及び全固体二次電池の製造方法、並びに、全固体二次電池用シート及び全固体二次電池
CN114497715A (zh) * 2022-04-13 2022-05-13 北京卫蓝新能源科技有限公司 一种电池用固含量稳定的无机氧化物固态电解质分散液及其制备方法和应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101232091B (zh) * 2007-01-24 2011-05-18 比亚迪股份有限公司 一种锂离子电池正极浆料的制备方法及电池
WO2012063827A1 (ja) * 2010-11-09 2012-05-18 株式会社村田製作所 全固体電池用スラリー、全固体電池用グリーンシート、全固体電池、および全固体電池用スラリーの製造方法
CN111498810B (zh) * 2019-01-31 2022-07-12 北京卫蓝新能源科技有限公司 一种纳米材料分散液及其制备方法
CN110071327A (zh) * 2019-04-10 2019-07-30 深圳新宙邦科技股份有限公司 一种固态电解质及聚合物锂离子电池

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109478685A (zh) * 2016-06-03 2019-03-15 富士胶片株式会社 固体电解质组合物、以及含固体电解质的片材、全固态二次电池、电极片及它们的制造方法
CN109301314A (zh) * 2017-07-24 2019-02-01 微宏动力系统（湖州）有限公司 一种无机固体电解质复合浆料的制备方法及无机固体电解质复合浆料
CN113841278A (zh) * 2019-05-31 2021-12-24 日本瑞翁株式会社 全固态二次电池用浆料组合物、含固态电解质层及全固态二次电池、以及全固态二次电池用浆料组合物的制造方法
WO2022004884A1 (ja) * 2020-07-02 2022-01-06 富士フイルム株式会社 全固体二次電池用シート及び全固体二次電池の製造方法、並びに、全固体二次電池用シート及び全固体二次電池
CN114497715A (zh) * 2022-04-13 2022-05-13 北京卫蓝新能源科技有限公司 一种电池用固含量稳定的无机氧化物固态电解质分散液及其制备方法和应用

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