CN114512711B - Inorganic oxide solid electrolyte nano dispersion liquid with stable solid content for battery and preparation method thereof - Google Patents
Inorganic oxide solid electrolyte nano dispersion liquid with stable solid content for battery and preparation method thereof Download PDFInfo
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- CN114512711B CN114512711B CN202210401967.5A CN202210401967A CN114512711B CN 114512711 B CN114512711 B CN 114512711B CN 202210401967 A CN202210401967 A CN 202210401967A CN 114512711 B CN114512711 B CN 114512711B
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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
- H01M10/0562—Solid materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
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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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses an inorganic oxide solid electrolyte nano dispersion liquid with stable solid content for a battery and a preparation method thereof. The inorganic oxide solid electrolyte nano dispersion liquid comprises inorganic oxide solid electrolyte nano particles, a solvent and a dispersing agent, wherein the dispersing agent is an ether dispersing agent with a special structure, and the solid content of the dispersion liquid is 40-85 wt%. The inorganic oxide solid electrolyte nano dispersion liquid uses a specific dispersant, so that the inorganic oxide solid electrolyte does not have the phenomenon of agglomeration during grinding and dispersion; and the inorganic oxide solid state electrolyte can be milled to smaller particle size particles under the same milling conditions; less solvent is used in the solid content range, and dispersion liquid with higher solid content and high stability can be obtained under the same condition, so that the requirements and the cost during preparation, storage and transportation can be reduced; the preparation method of the inorganic nano dispersion liquid is simple and is suitable for large-scale production.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to inorganic oxide solid electrolyte nano dispersion liquid with stable solid content for batteries and a preparation method thereof.
Background
A part of inorganic oxide solid electrolyte is often used in the battery to replace combustible electrolyte, and the application can reduce the usage amount of the electrolyte, thereby reducing the heat release of thermal runaway of the battery and improving the safety performance; on the other hand, the inorganic oxide solid electrolyte has certain lithium ion conductivity, and can provide lithium ion conductivity after replacing an electrolyte, so that the rate performance of the battery is maintained.
The method for introducing the nanoscale inorganic oxide solid electrolyte into the battery is usually applied to the modification of a pole piece or a diaphragm coating, and the inorganic solid electrolyte needs to be prepared into nano powder or nano dispersion liquid. When the nano powder is directly used, the nano powder is poor in dispersibility after being added into a system, and nano powder particles are easy to agglomerate; when used in the form of a nano dispersion, a uniformly dispersed nanoparticle system is easily obtained, and thus the nano dispersion is more widely used.
However, during storage and use of the dispersion, the inorganic oxide solid electrolyte is liable to settle at the bottom of the container due to gravity and interparticle interaction, resulting in non-uniform solid contents of the upper and lower layers of the dispersion, i.e., poor stability of the solid content of the dispersion. This causes a serious problem in the actual production process. Firstly: the solid content of the existing dispersion liquid is generally less than 30%, and more than 70% of solvent is an ineffective component which is volatilized finally, so that the cost of raw materials is increased; secondly, the method comprises the following steps: more than 70% of the solvent in the dispersion liquid occupies a large amount of mass proportion, and the transportation cost is increased; and thirdly: part of the solvent is flammable and explosive organic solvent, the mass ratio reaches more than 70 percent, and risks exist during storage and transportation; fourthly: when the dispersion liquid is stored, the solid content characteristic is changed, the speed is high, the solid content characteristic basically occurs within 24 hours, the transportation process of the dispersion liquid is basically longer than 24 hours, and the storage time required by product inventory is longer than 30 days, so that the product cannot be used as inventory storage, and risks are brought to production planning; and finally: the existing situation is that the product is prepared for use at present, and can be used within a short time (24 hours) reluctantly, but in the actual large-scale production process, when the material is loaded in the form of dispersion liquid, the time that the material can be stored in a pipeline is longer than 24 hours, so that solid particles in the dispersion liquid are settled in the loading pipeline, the loading value cannot be accurately determined, and the consistency of the product is influenced. The above disadvantages seriously hinder the large-scale application of inorganic oxide electrolytes, and new methods need to be developed to solve the above problems. At present, methods for improving the solid content stability of a dispersion liquid and preventing sedimentation mainly comprise methods of adding a dispersing agent and centrifuging.
Patent CN102760510B describes an ATO nanocrystal aqueous dispersion with high purity, high solid content, good transparency, excellent conductivity, stable storage, no agglomeration and no sedimentation without using any auxiliary agent. The method comprises the steps of grinding through a sand mill, carrying out ultrasonic crushing and dispersing to prepare a common ATO water system dispersion liquid, and then carrying out high-speed centrifugation on the dispersion liquid to obtain a supernatant liquid with small granularity. The process is believed to improve the stability of the dispersion at low solids content. The method has the advantages that no auxiliary agent is used, the sedimentation of large particles is accelerated by a centrifugal method, and small particles in the supernatant are more stable and are not easy to settle. The method has the disadvantages that the solid content of the centrifuged supernatant is reduced, the centrifuged lower-layer solid is easy to agglomerate, the dispersion liquid needs to be obtained by multi-stage crushing again, the process is complex, and the efficiency of the whole process is low. And the dispersion prepared by the method has low solid content, thereby greatly increasing the transportation cost.
Patent CN201810560205.3 describes a method for preparing Zn with stable solid content by using a dispersing agent in combination with a low-temperature centrifugation technology 2 TiO 4 A method for producing a dispersion which comprises subjecting a dispersion to a centrifugal treatment to obtain a dispersion having a high and stable solid content. However, the method has the phenomenon of solid content gradient distribution in the centrifugal process, and the whole solid content uniformity of the slurry is poor.
Patent CN114156600A describes a method for preparing inorganic oxide solid electrolyte dispersion for coating the surface of a separator. The method comprises the steps of mixing inorganic oxide solid electrolyte with a solvent, sanding uniformly, and adding 5wt% of wetting agent, 5wt% of dispersing agent, 20 wt% of binder and 5wt% of auxiliary agent to prepare dispersion liquid slurry for coating the diaphragm. The dispersion slurry can achieve the effect of uniform particle size distribution, but cannot achieve the effect of stable solid content, and various dispersants are used, so that the purity of a system is influenced.
Generally speaking, the prior art can not meet the requirements of simple process, stable solid content, good redispersibility, low transportation cost and no additive at the same time.
Disclosure of Invention
Aiming at the limitations of the technology, the invention uses a simple grinding method, and uses a solvent with polarity of 4-8 and an ether dispersant with a special structure in an inorganic oxide solid electrolyte nano dispersion liquid to prepare the solid electrolyte dispersion liquid with solid content of 40-85 wt% and granularity of 50-1000 nm, thereby achieving the effects of long-time storage and stability of granularity and solid content.
The inorganic oxide solid electrolyte nano dispersion liquid with stable solid content for the battery consists of inorganic oxide solid electrolyte particles, an organic solvent and a dispersing agent.
The solid content of the inorganic oxide solid electrolyte nano dispersion liquid is 40-85 wt%. The solid content means a mass ratio of the solid electrolyte in the dispersion liquid.
The mass ratio of the solvent to the inorganic oxide solid electrolyte particles to the dispersing agent in the inorganic oxide solid electrolyte nano dispersion liquid is (17-150): 100: (0.2-10).
The dispersant has at least one of the following structural formulas:
wherein A is 1 、A 2 、A 3 Is independently-H or-OH, and the structural formulas (I) and (II) at least contain one-OH functional group; x, X 1 、X 2 、X 3 、Y、Y 1 、Y 2 、Y 3 Independently is
Wherein R1 and R2 may be the same or different, and R1 and R2 are H, CH 3 Or CH 2 CH 3 . The molecular weight range of the dispersant is as follows: 1000 to 30000 Da.
The inorganic oxide solid electrolyte is selected from 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 Al(PO 4 )O 1- y M 2y 、LiAlPO 4 F x3 (OH) 1-x3 、Na-β/β″-Al 2 O 3 Wherein M1 is at least one of Nb, Ta and Sb, M is at least one of F, Cl, Br and I, x1 is more than or equal to 0 and less than or equal to 0.7, and x2 is more than or equal to 0 and less than or equal to 0<1，0≤x3<1，0<y<0.1；
Preferably, the inorganic oxide solid electrolyte is Li 1+x4+n Al x4 Ti 2-x4 Si n (P 1-n/3 O 4 ) 3 、Li 1+x4+n Al x4 Ge 2- x4 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 1-x2 Al(PO 4 )O 1-y M 2y 、LiAlPO 4 F x3 (OH) 1-x3 、Na-β/β″-Al 2 O 3 Wherein M1 is at least one of Nb, Ta and Sb, M is at least one of F, Cl, Br and I, A2 is any one of Nb, Ta and W, 0-0 x 1-0.7, 0-0 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。
The solvent is selected from aprotic solvents with a polarity value of 4-8.
The viscosity of the inorganic oxide solid electrolyte nano dispersion liquid is 200 mPa.S-10000 mPa.S.
Preferably, the solvent is at least one of NMP, DMSO, DMAc, and DMF.
The size of the inorganic oxide solid electrolyte nano-particles is 50nm-1 μm, and the particle size refers to the D50 test result of the dispersion liquid.
After the inorganic oxide solid electrolyte nano dispersion liquid is stood for 30 days, the solid content change value of the dispersion liquid is less than 2 percent.
After the inorganic oxide solid electrolyte nano dispersion liquid is stood for 30 days, the particle size change rate of the inorganic oxide solid electrolyte nano particles is less than 5 percent.
Another aspect of the present invention is to provide a method for preparing an inorganic oxide solid electrolyte nano dispersion, comprising the steps of:
(1) mixing: adding a grinding medium, inorganic oxide solid electrolyte powder, a solvent and a dispersing agent into a grinding cavity, and uniformly stirring to obtain dispersion liquid slurry.
(2) Grinding: and grinding the grinding medium, the inorganic oxide solid electrolyte powder, the solvent and the dispersing agent which are mixed in the grinding cavity to obtain the inorganic oxide solid electrolyte nano dispersion liquid.
The grinding preparation method has the functions of crushing and ultrasonic dispersion, and the ultrasonic dispersion cannot achieve the same effect.
The grinding method is a grinding method having a crushing function, and is preferably ball mill grinding, vertical stirring mill grinding, sand mill grinding, and barrel ball mill grinding.
Preferably, the mass ratio of the grinding medium, the solvent, the inorganic oxide solid electrolyte powder and the dispersing agent is (2000-100): (17-150): 100: (0.2-10).
Preferably, the milling time is from 30 minutes to 100 hours.
Preferably, the linear grinding speed is more than or equal to 3 m/s.
The invention also provides application of the inorganic oxide solid electrolyte nano dispersion liquid in batteries, including application in liquid batteries, solid-liquid mixed batteries and solid-state battery mixed solid-liquid batteries.
The invention also provides application of the inorganic oxide solid electrolyte nano dispersion liquid in a positive electrode and a diaphragm of a battery, which comprises diluting and applying the inorganic oxide solid electrolyte nano dispersion liquid in pole piece blending, pole piece surface coating, diaphragm surface coating and electrode particle surface coating.
The invention uses simple grinding method, uses high-polarity solvent and special dispersant, controls the solid content range of the system, obtains inorganic oxide solid electrolyte nano dispersion liquid with stable granularity and degree content, reduces transportation cost and improves the accuracy of the dispersion liquid.
The technical principle is as follows: first, ether dispersants of a specific structure are used, which contain a large number of hydroxyl and ether functional groups, as well as pendant alkane chains. The ether bond and hydroxyl functional group in the dispersant and the hydroxyl or polar group on the surface of the electrolyte particle are subjected to hydrogen bond and polar interaction and are anchored on the surface of the particle. The nonpolar functional group interacts with the organic solvent, so that the surface energy among particles is reduced, the particles are smaller after grinding, the particle size range of 50nm-1000nm can be reached, and the particles are not agglomerated after long-time storage; secondly, the solid content of the dispersion liquid is improved, the proportion of free solvent in the dispersion liquid is reduced, the proportion of combined solvent in the dispersion liquid is improved, and the alkane chain of the dispersant is interacted between the surfaces of adjacent particles, so that the diffusion difficulty of the inorganic oxide solid electrolyte is increased, and the effect of improving the stability of the solid content is achieved; finally, the dispersant can be used in a high solid content system to reduce the viscosity of the dispersion liquid, further improve the upper limit of the solid content of the dispersion liquid, improve the production efficiency and reduce the production difficulty.
Compared with the prior art, the invention has the following advantages and prominent effects:
the invention uses the grinding method to prepare the inorganic oxide solid electrolyte nano dispersion liquid with stable solid content, has the same process as the prior method, and is suitable for large-scale production. Compared with the processes such as centrifugation, the solid content of the prepared dispersion liquid is uniform, the crushing effect is considered in the preparation process, the requirement on the granularity of the raw material is lower, and the process is simple.
The inorganic oxide solid electrolyte nano dispersion liquid prepared by the invention has high solid content, and compared with the existing dispersion liquid with low solid content, the inorganic oxide solid electrolyte nano dispersion liquid reduces the using amount of a solvent, thereby reducing the cost of raw materials and the transportation cost, reducing the potential safety hazard and improving the production efficiency.
The dispersion liquid has high solid content stability, does not settle in the processes of storage, transportation and feeding, and solves the problems that the stock cannot be stored and the feeding amount is not accurate.
The inorganic oxide solid electrolyte nano dispersion liquid prepared by the invention uses a specific dispersing agent at the same time, so that the viscosity of the dispersion liquid can be reduced, the solid content upper limit of the dispersion liquid is further improved, and the stable effect of the dispersion liquid is kept; while the abrasive particle size can be further reduced under the same grinding conditions.
The invention has low requirements on the particle size and the morphology of the particles, and can improve the stability of solid content without inorganic oxide solid electrolyte particles with extremely small particle size or special morphology.
The dispersant used in the invention is added into the battery, and has no negative influence on the performance of the battery.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The method for testing the solid content stability of the dispersion liquid comprises the following steps:
the solid content of the dispersion liquid is tested by using a drying method, and the solid content stability test steps are as follows:
(1) the prepared dispersion was taken to test solids content and recorded as initial solids content w 0.
(2) 100mL of the dispersion was taken out into a 150mL vial, and the vial was sealed and allowed to stand for 30 days. After 30 days, 1mL of the dispersion in the flask at a distance of 5mm from the liquid surface was taken and the solids content was measured and recorded as w 1. Taking 1mL of the dispersion in the experimental bottle at a position 5mm away from the bottom of the bottle, testing the solid content, and recording as a solid content value w2 of the lower layer of the dispersion.
(3) The dispersion solid content stability is measured by the deviation of the upper and lower layer solid content values w1 and w2 from the initial solid content value w 0. Wherein the solid content of the upper layer has a variation value of S1 ═ w1-w0|/w0 × 100%, and the solid content of the lower layer has a variation value of S2 ═ w2-w0|/w0 × 100%, and the smaller the values of S1 and S2 indicate the more stable the slurry.
The method for testing the particle size stability of the dispersion comprises the following steps:
the particle size of the dispersion is tested by using a nanometer particle size analyzer, the solvent used in the test is consistent with the solvent of the dispersion, and the particle size stability test comprises the following steps:
(1) the prepared dispersion was taken to test particle size and recorded as initial average particle size D0.
(2) 100mL of the dispersion was taken out into a 150mL vial, and the vial was sealed and allowed to stand for 30 days. After 30 days, 1mL of the dispersion in the flask at a distance of 5mm from the liquid surface was taken, and the particle size was measured and recorded as the upper particle size D1 of the dispersion. Taking 1mL of the dispersion liquid in the experimental bottle at a position 5mm away from the bottom of the bottle, testing the particle size, and recording as the particle size value D2 of the lower layer of the dispersion liquid.
(3) The dispersion particle stability was measured by the deviation of the particle size values D1, D2 of the upper and lower layers from the initial particle size value D0. Wherein, the particle size change value of the upper layer of the slurry is T1 ═ D1-D0|/D0 × 100%, the particle size change value of the lower layer is T2 ═ D2-D0|/D0 × 100%, and the smaller the values of T1 and T2 are, the more stable the particle size of the dispersion is.
Example 1
The method comprises the following steps: 500 parts by weight of zirconium balls and 100 parts by weight of Li having a particle diameter of 3 μm 7 La 3 Zr 2 O 12 Oxide solid electrolyte powder, 43 parts by weight of NMP solvent and 1 part by weight of dispersant
Adding into the cavity, and stirring.
Step two: mixing zirconium balls and Li in the cavity 7 La 3 Zr 2 O 12 Sanding the powder, NMP and a dispersing agent to obtain slurry with the solid content of 70 percent and the D50 of 200nm, wherein the grinding time is 4 hours, and the grinding linear speed is 8 m/s;
the prepared dispersion was subjected to a dispersion solid content stability test and a dispersion particle size stability test, and the results are shown in tables 1 and 2.
The prepared dispersion can be blended into a positive electrode for use.
Example 2
The method comprises the following steps: 500 parts by weight of zirconium balls and 100 parts by weight of Li having a particle diameter of 4 μm 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Oxide solid electrolyte powder, 43 parts by weight of DMF solvent and 0.2 part by weight of dispersant
Adding into the cavity, and stirring.
Step two: mixing zirconium balls and Li in a grinding cavity 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Sanding the powder, DMF and a dispersing agent to obtain slurry with the solid content of 70 percent and the D50 of 200nm, wherein the grinding time is 5 hours and the grinding linear speed is 7 m/s;
the prepared dispersion was subjected to a dispersion solid content stability test and a dispersion particle size stability test, and the results are shown in tables 1 and 2.
The prepared dispersion liquid is blended in a positive electrode for use.
Example 3
The method comprises the following steps: 500 parts by weight of zirconium balls and 100 parts by weight of Li having a particle diameter of 5 μm 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Oxide solid electrolyte powder, 43 parts by weight of NMP solvent and 1 part by weight of dispersant
Adding into the cavity, and stirring.
Step two: mixing zirconium balls and Li in the cavity 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Grinding the powder, NMP and a dispersing agent to obtain slurry with the solid content of 70% and the D50 of 200nm, wherein the grinding time is 4.5 hours, and the grinding linear speed is 7 m/s;
the prepared dispersion was subjected to a dispersion solid content stability test and a dispersion particle size stability test, and the results are shown in tables 1 and 2.
The prepared dispersion liquid is blended in a positive electrode for use.
Example 4
The method comprises the following steps: 500 parts by weight of zirconium balls and 100 parts by weight of Li having a particle diameter of 3 μm 0.35 La 0.55 TiO 3 Oxide solid electrolyte powder, 43 parts by weight of DMSO solvent and 3 parts by weight of dispersant
Adding into the cavity, and stirring.
Step two: mixing zirconium balls and Li in the cavity 0.35 La 0.55 TiO 3 Grinding the powder, DMSO and a dispersing agent to obtain slurry with the solid content of 70% and the D50 of 200nm, wherein the grinding time is 4.5 hours, and the grinding linear velocity is 6.5 m/s;
the prepared dispersion was subjected to a dispersion solid content stability test and a dispersion particle size stability test, and the results are shown in tables 1 and 2.
The prepared dispersion liquid is coated on the surface of the positive pole piece.
Example 5
The method comprises the following steps: 500 parts by weight of zirconium balls and 100 parts by weight of LiTiOPO having a particle diameter of 3 μm 4 Oxide solid electrolyte powder, 43 parts by weight of DMAc solvent and 5 parts by weight of dispersant
Adding into grinding chamber, and stirring.
Step two: mixing the zirconium balls and the LiTiOPO in a grinding cavity 4 Grinding the powder, DMAc and a dispersing agent to obtain slurry with the solid content of 70% and the D50 of 200nm, wherein the grinding time is 5 hours, and the grinding linear speed is 6.8 m/s;
the prepared dispersion was subjected to a dispersion solid content stability test and a dispersion particle size stability test, and the results are shown in tables 1 and 2.
The prepared dispersion liquid is blended in a positive electrode for use.
Example 6
The method comprises the following steps: will be provided with500 parts by weight of zirconium balls, 100 parts by weight of Li having a particle diameter of 2.5 μm 7 La 3 Zr 2 O 12 Oxide solid electrolyte powder, 150 parts by weight of NMP solvent and 1 part by weight of dispersant
Adding into grinding cavity, and stirring.
Step two: mixing zirconium balls and Li in a grinding cavity 7 La 3 Zr 2 O 12 Grinding the powder, NMP and a dispersing agent to obtain slurry with the solid content of 40% and the D50 of 200nm, wherein the grinding time is 3.5 hours, and the grinding linear speed is 6.7 m/s;
the prepared dispersion was subjected to a dispersion solid content stability test and a dispersion particle size stability test, and the results are shown in tables 1 and 2.
The prepared dispersion liquid is blended in a positive electrode for use.
Example 7
The method comprises the following steps: 500 parts by weight of zirconium balls and 100 parts by weight of Li having a particle diameter of 3 μm 7 La 3 Zr 2 O 12 Oxide solid electrolyte powder, 100 parts by weight of NMP solvent and 1 part by weight of dispersant
Adding into grinding chamber, and stirring.
Step two: mixing zirconium balls and Li in a grinding cavity 7 La 3 Zr 2 O 12 Grinding the powder, NMP and a dispersing agent to obtain slurry with the solid content of 50 percent and the D50 of 200nm, wherein the grinding time is 4 hours and the grinding linear speed is 6.8 m/s;
the prepared dispersion was subjected to a dispersion solid content stability test and a dispersion particle size stability test, and the results are shown in tables 1 and 2.
The prepared dispersion liquid is coated on the surface of the diaphragm for use.
Example 8
The method comprises the following steps: 500 parts by weight of zirconium balls and 100 parts by weight of Li having a particle diameter of 3 μm 7 La 3 Zr 2 O 12 Oxide compoundSolid electrolyte powder, 18 parts by weight of NMP solvent and 1 part by weight of dispersant
Adding into grinding chamber, and stirring.
Step two: mixing zirconium balls and Li in a grinding cavity 7 La 3 Zr 2 O 12 Grinding the powder, NMP and a dispersing agent to obtain slurry with the solid content of 85 percent and the D50 of 200nm, wherein the grinding time is 6 hours, and the grinding linear speed is 6.9 m/s;
the prepared dispersion was subjected to a dispersion solid content stability test and a dispersion particle size stability test, and the results are shown in tables 1 and 2.
The prepared dispersion is blended in a positive electrode for use.
Example 9
The method comprises the following steps: 500 parts by weight of zirconium balls and 100 parts by weight of Li having a particle diameter of 10 μm 7 La 3 Zr 2 O 12 Oxide solid electrolyte powder, 43 parts by weight of NMP solvent and 1 part by weight of dispersant
Adding into vertical stirring mill, and stirring.
Step two: mixing zirconium balls and Li in a grinding cavity 7 La 3 Zr 2 O 12 Grinding the powder, NMP and a dispersing agent to obtain slurry with the solid content of 70% and the D50 of 1000nm, wherein the grinding time is 5 hours, and the grinding linear speed is 4.8 m/s;
the prepared dispersion was subjected to a dispersion solid content stability test and a dispersion particle size stability test, and the results are shown in tables 1 and 2.
The prepared dispersion liquid is blended in a positive electrode for use.
Example 10
The method comprises the following steps: 500 parts by weight of zirconium balls and 100 parts by weight of Li having a particle diameter of 4 μm 7 La 3 Zr 2 O 12 Oxide solid electrolyte powder, 43 parts by weight of NMP solvent and 1 part by weight of dispersant
Adding into grinding chamber of roller ball mill, and stirring.
Step two: mixing zirconium balls and Li in a grinding cavity 7 La 3 Zr 2 O 12 Grinding the powder, NMP and a dispersing agent to obtain slurry with the solid content of 70% and the D50 of 800nm, wherein the grinding time is 5 hours, and the grinding linear speed is 5.1 m/s;
the prepared dispersion was subjected to a dispersion solid content stability test and a dispersion particle size stability test, and the results are shown in tables 1 and 2.
The prepared dispersion liquid is blended in a positive electrode for use.
Example 11
The method comprises the following steps: 500 parts by weight of zirconium balls and 100 parts by weight of Li having a particle diameter of 3 μm 7 La 3 Zr 2 O 12 Oxide solid electrolyte powder, 43 parts by weight of NMP solvent and 1 part by weight of dispersant
Adding into grinding chamber, and stirring.
Step two: mixing zirconium balls and Li in a grinding cavity 7 La 3 Zr 2 O 12 Grinding the powder, NMP and a dispersing agent to obtain slurry with the solid content of 70% and the D50 of 500nm, wherein the grinding time is 5 hours, and the grinding linear speed is 5.3 m/s;
the prepared dispersion was subjected to a dispersion solid content stability test and a dispersion particle size stability test, and the results are shown in tables 1 and 2.
The prepared dispersion liquid is blended in a positive electrode for use.
Example 12
The method comprises the following steps: 500 parts by weight of zirconium balls and 100 parts by weight of Li having a particle diameter of 5 μm 7 La 3 Zr 2 O 12 Oxide solid electrolyte powder, 43 parts by weight of NMP solvent and 1 part by weight of dispersant
Adding into the cavity of the sand mill, and stirring uniformly.
Step two: mixing zirconium balls and Li in the cavity 7 La 3 Zr 2 O 12 Grinding the powder, NMP and a dispersing agent to obtain slurry with the solid content of 70% and the D50 of 100nm, wherein the grinding time is 7.5 hours, and the grinding linear speed is 9 m/s;
the prepared dispersion was subjected to a dispersion solid content stability test and a dispersion particle size stability test, and the results are shown in tables 1 and 2.
The prepared dispersion liquid is blended in a positive electrode for use.
Comparative example 1
The method comprises the following steps: 500 parts by weight of zirconium balls and 100 parts by weight of Li having a particle diameter of 3 μm 7 La 3 Zr 2 O 12 Adding oxide solid electrolyte powder and 43 parts by weight of NMP solvent into a grinding cavity, and uniformly stirring.
Step two: mixing zirconium balls and Li in a grinding cavity 7 La 3 Zr 2 O 12 Grinding the powder and NMP to obtain slurry with the solid content of 70 percent and the D50 of 300nm, wherein the grinding time is 6.5 hours, and the grinding linear speed is 8 m/s;
the prepared dispersion was subjected to a dispersion solid content stability test and a dispersion particle size stability test, and the results are shown in tables 1 and 2.
The prepared dispersion liquid is blended in a positive electrode for use.
Comparative example 2
The method comprises the following steps: 500 parts by weight of zirconium balls and 100 parts by weight of LiTiOPO having a particle size of 4 μm 4 Adding oxide solid electrolyte powder, 300 parts by weight of NMP solvent and 1 part by weight of sodium dodecyl benzene sulfonate additive into a grinding cavity, and uniformly stirring.
Step two: mixing the zirconium balls and the LiTiOPO in a grinding cavity 4 Grinding the powder, NMP and a sodium dodecyl benzene sulfonate additive to obtain slurry with the solid content of 25 percent and the D50 of 200nm, wherein the grinding time is 5 hours, and the grinding linear speed is 6.8 m/s;
the prepared dispersion was subjected to a dispersion solid content stability test and a dispersion particle size stability test, and the results are shown in tables 1 and 2.
The prepared dispersion liquid is blended in a positive electrode for use.
Comparative example 3
The method comprises the following steps: 500 parts by weight of zirconium balls and 100 parts by weight of Li with the particle size of 200nm 7 La 3 Zr 2 O 12 Oxide solid electrolyte powder, 43 parts by weight of NMP solvent and 1 part by weight of additive
Adding into a PP plastic barrel with the size of 1L, and sealing with a sealing film.
Step two: and (3) carrying out ultrasonic treatment on the dispersion liquid in the sealed plastic barrel for 5 hours. Because the ultrasonic wave has no shearing effect and the viscosity of the dispersion liquid is high, the agglomerated particles cannot be completely opened, the electrolyte particles still keep an agglomerated state, and finally the slurry with the solid content of 70 percent and the D50 of 1000nm is obtained;
the prepared dispersion was subjected to a dispersion solid content stability test and a dispersion particle size stability test, and the results are shown in tables 1 and 2.
The prepared dispersion liquid is blended in a positive electrode for use.
Comparative example 4
The method comprises the following steps: 500 parts by weight of zirconium balls and 100 parts by weight of Li having a particle diameter of 5 μm 7 La 3 Zr 2 O 12 Oxide solid electrolyte powder, 400 parts by weight of NMP solvent and 1 part by weight of dispersant
Adding into grinding chamber, and stirring.
Step two: mixing zirconium balls and Li in a grinding cavity 7 La 3 Zr 2 O 12 Grinding the powder, NMP and a dispersing agent to obtain slurry with the solid content of 20 percent and the D50 of 200nm, wherein the grinding time is 4.5 hours, and the grinding linear speed is 6.8 m/s;
the prepared dispersion was subjected to a dispersion solid content stability test and a dispersion particle size stability test, and the results are shown in tables 1 and 2.
The prepared dispersion liquid is blended in a positive electrode for use.
Comparative example 5
The method comprises the following steps: 500 parts by weight of zirconium balls and 100 parts by weight of Li having a particle diameter of 30 μm 7 La 3 Zr 2 O 12 Oxide solid electrolyte powder, 100 parts by weight of NMP solvent and 1 part by weight of dispersant
Adding into a vertical stirring mill grinding cavity, and stirring uniformly.
Step two: mixing zirconium balls and Li in a grinding cavity 7 La 3 Zr 2 O 12 Grinding the powder, NMP and a dispersing agent to obtain slurry with the solid content of 50% and the D50 of 5000nm, wherein the grinding time is 3 hours, and the grinding linear speed is 4.2 m/s;
the prepared dispersion was subjected to a dispersion solid content stability test and a dispersion particle size stability test, and the results are shown in tables 1 and 2.
The prepared dispersion liquid is blended in a positive electrode for use.
TABLE 1 stability test results for solid content of dispersion
TABLE 2 particle size stability test results for dispersions
Compared with the comparative example group and the comparative example group, when the solid content is 40wt% -85 wt%, the particle size is 50nm-1000nm, and the dispersant of the patent is used, the solid content stability of the dispersion liquid is good; comparing example 1 with examples 6 to 8, the higher the solid content, the more stable the solid content of the dispersion; comparing example 1 and examples 9-12, the smaller the particle size, the more stable the solids content. When the sodium dodecyl benzene sulfonate is used as the dispersant with the solid content of 20 percent, the solid content stability of the dispersion liquid is also poor, and the S1 and S2 values are far more than 2 percent. When the ultrasonic method is used for dispersion, the requirement on the feeding granularity is high and is the same as the discharging granularity because the ultrasonic treatment does not have shearing action and can not break the electrolyte particles. And because the viscosity value of the dispersion liquid is high, the particles are still in an agglomerated state after being treated by the ultrasonic method, so that the agglomerated particles in the dispersion liquid are rapidly settled.
The dispersion liquid prepared in the embodiment is mixed in a positive electrode for use, or coated on the surface of a positive electrode pole piece for use, or coated on the surface of a positive electrode material for use, so that the electrical property and the safety performance of the battery can be improved.
It will be understood that the above embodiments are merely exemplary embodiments taken to illustrate the principles of the present invention, which is not limited thereto. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit and substance of the invention, and these modifications and improvements are also considered to be within the scope of the invention.
Claims (11)
1. An inorganic oxide solid electrolyte nano dispersion liquid with stable solid content for batteries is characterized in that:
the inorganic oxide solid electrolyte nano dispersion liquid consists of inorganic oxide solid electrolyte particles, an organic solvent and a dispersing agent;
the solid content of the inorganic oxide solid electrolyte nano dispersion liquid is 40-85 wt%;
the mass ratio of the solvent to the inorganic oxide solid electrolyte particles to the dispersing agent in the inorganic oxide solid electrolyte nano dispersion liquid is (17-150): 100: (0.2-10);
the dispersant has at least one of the following structural formulas:
(I)、
(II)、
wherein A is 1 、A 2 、A 3 Is independently-H or-OH, and the structural formulas (I) and (II) at least contain one-OH functional group; x, X 1 、X 2 、X 3 、Y、Y 1 、Y 2 、Y 3 Independently is
Wherein R is 1 、R 2 Independently is-H, -CH 3 or-CH 2 CH 3 ；
The molecular weight range of the dispersant is as follows: 1000 to 30000 Da.
2. The inorganic oxide solid state electrolyte nanodispersion as claimed in claim 1, wherein:
the inorganic oxide solid electrolyte is selected from 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 Al(PO 4 )O 1-y M 2y 、LiAlPO 4 F x3 (OH) 1-x3 、Na-β/β″-Al 2 O 3 Wherein M1 is at least one of Nb, Ta and Sb, M is at least one of F, Cl, Br and I, x1 is more than or equal to 0 and less than or equal to 0.7, and x2 is more than or equal to 0 and less than or equal to 0<1，0≤x3<1，0<y<0.1；
The solvent is selected from aprotic solvents with a polarity value ranging from 4 to 8.
3. The inorganic oxide solid state electrolyte nanodispersion of claim 2, wherein the inorganic oxide solid state electrolyte is Li 1+x4+n Al x4 Ti 2-x4 Si n (P 1-n/3 O 4 ) 3 、Li 1+x4+n Al x4 Ge 2-x4 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 1-x2 Al(PO 4 )O 1-y M 2y 、LiAlPO 4 F x3 (OH) 1-x3 、Na-β/β″-Al 2 O 3 Wherein M1 is at least one of Nb, Ta and Sb, M is at least one of F, Cl, Br and I, A2 is any one of Nb, Ta and W, 0-0 x 1-0.7, 0-0 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。
4. The inorganic oxide solid state electrolyte nanodispersion of claim 1, wherein the solvent is at least one of NMP, DMSO, DMAc, DOL and DMF.
5. The inorganic oxide solid state electrolyte nanodispersion as claimed in claim 1, wherein the solid content is 50wt% to 80 wt%.
6. The inorganic oxide solid state electrolyte nanodispersion as claimed in claim 1, wherein:
in the inorganic oxide solid electrolyte nano dispersion liquid, the size of inorganic oxide solid electrolyte nano particles is 50nm-1 mu m.
7. The inorganic oxide solid state electrolyte nanodispersion of claim 1, wherein:
after the inorganic oxide solid electrolyte nano dispersion liquid is stood for 30 days, the solid content change value of the dispersion liquid is less than 2 percent.
8. A method for preparing an inorganic oxide solid state electrolyte nanodispersion as claimed in any one of claims 1-7, comprising the steps of:
(1) mixing: adding a grinding medium, inorganic oxide solid electrolyte powder, a solvent and a dispersing agent into a grinding cavity to obtain dispersion slurry;
(2) grinding: and grinding the grinding medium, the inorganic oxide solid electrolyte powder, the solvent and the dispersing agent which are mixed in the grinding cavity to obtain the inorganic oxide solid electrolyte nano dispersion liquid.
9. The method of claim 8, wherein:
in the dispersion liquid slurry, the mass ratio of a grinding medium, a solvent, inorganic oxide solid electrolyte powder and a dispersing agent is (2000-100): (17-150): 100: (0.2-10).
10. Use of the inorganic oxide solid electrolyte nanodispersion as claimed in any one of claims 1 to 7 in batteries, including liquid batteries, solid-liquid hybrid batteries and solid-state batteries.
11. Use of the inorganic oxide solid state electrolyte nanodispersion of any one of claims 1-7 in a positive electrode and separator in a battery.
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