CN117013059A - Inorganic oxide solid electrolyte dispersion liquid with stable solid content - Google Patents
Inorganic oxide solid electrolyte dispersion liquid with stable solid content Download PDFInfo
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- 239000006185 dispersion Substances 0.000 title claims abstract description 203
- 239000007787 solid Substances 0.000 title claims abstract description 128
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 84
- 229910052809 inorganic oxide Inorganic materials 0.000 title claims abstract description 81
- 239000007788 liquid Substances 0.000 title claims abstract description 70
- 239000002245 particle Substances 0.000 claims abstract description 90
- 238000000227 grinding Methods 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002904 solvent Substances 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 15
- 230000008859 change Effects 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 229910009274 Li1.4Al0.4Ti1.6 (PO4)3 Inorganic materials 0.000 claims description 3
- 239000011324 bead Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000003586 protic polar solvent Substances 0.000 claims description 3
- 229910009178 Li1.3Al0.3Ti1.7(PO4)3 Inorganic materials 0.000 claims description 2
- 229910005317 Li14Zn(GeO4)4 Inorganic materials 0.000 claims description 2
- 239000002228 NASICON Substances 0.000 claims description 2
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 7
- 239000002001 electrolyte material Substances 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- 230000000996 additive effect Effects 0.000 abstract 1
- 238000013112 stability test Methods 0.000 description 44
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 38
- 229910052726 zirconium Inorganic materials 0.000 description 38
- 239000010936 titanium Substances 0.000 description 33
- 239000002002 slurry Substances 0.000 description 32
- 238000003801 milling Methods 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 20
- 239000002270 dispersing agent Substances 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 238000000576 coating method Methods 0.000 description 10
- 238000004062 sedimentation Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000010954 inorganic particle Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 238000001132 ultrasonic dispersion Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910007857 Li-Al Inorganic materials 0.000 description 1
- 229910008447 Li—Al Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000000010 aprotic solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000010951 particle size reduction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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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
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to the technical field of lithium batteries, and discloses an inorganic oxide solid electrolyte dispersion liquid with stable solid content, which is obtained by mixing an inorganic oxide solid electrolyte and a solvent according to a certain proportion and grinding. The solvent in the dispersion liquid is a proton solvent, and the inorganic oxide solid electrolyte is an electrolyte material which does not or is not easy to dissociate lithium ions. The inorganic oxide solid electrolyte dispersion can be used for lithium ion batteries, and has good compatibility with the existing working procedure using water as a solvent. Meanwhile, the dispersion liquid prepared by the invention has no additive, and inorganic oxide solid electrolyte in the dispersion liquid does not settle or agglomerate after the dispersion liquid is kept stand for a long time, so that the problems of particle settlement during transportation, storage and feeding of the inorganic oxide solid electrolyte dispersion liquid in battery production are solved.
Description
Technical field:
the invention relates to the technical field of lithium batteries, in particular to an inorganic oxide solid electrolyte dispersion liquid with stable solid content for a lithium battery and a preparation method thereof.
The background technology is as follows:
the solid-liquid mixed lithium ion battery is an advanced technology developed in the current battery field, and the inorganic oxide solid electrolyte is utilized to replace part of organic electrolyte, so that not only can the energy density be improved, but also the safety of the battery can be improved. The safety problem of the high-silicon negative electrode is remarkable, and in order to improve the safety of the negative electrode, a solid electrolyte needs to be coated on the surface of a negative electrode plate. When the inorganic oxide solid electrolyte is coated on the surface of the negative electrode sheet, it is required to process the negative electrode sheet into a dispersion. In order to improve the wetting effect of the solid electrolyte coating and the cathode, a proton type solvent is used as a solvent of the inorganic oxide solid electrolyte dispersion liquid in the synchronous coating process, so that the compatibility with slurry is good, and the coating effect is better.
The protic solvent is typically a compound containing a hydroxyl group or an amino group, such as: deionized water, ethanol, ethylene glycol, isopropanol, and the like, which can provide lone pair electrons and protons; the surface of an inorganic oxide solid electrolyte typically contains a large number of oxygen atoms or dangling hydrogen bonds that adsorb in air. The hydroxyl or amino functional group of the proton solvent interacts with the inorganic oxide solid electrolyte to form a hydrogen bond, which is favorable for uniform and stable dispersion in the solvent, so that the proton solvent is used for dispersion in the inorganic oxide solid electrolyte dispersion liquid, and the stability of the system is good. However, part of the inorganic oxide solid electrolyte is easy to dissociate lithium ions, protons provided by the proton solvent can promote the precipitation of lithium ions, so that Li-H exchange is more serious, the surface charge state of the inorganic oxide solid electrolyte is affected, particle aggregation is caused, the dispersion difficulty is increased, the stability of a dispersion liquid is reduced, and the inorganic oxide solid electrolyte shows strong alkalinity in water. Therefore, the inorganic oxide solid electrolyte needs to be subjected to species screening, and Li-H exchange weak electrolyte is used, so that the inorganic oxide solid electrolyte with the pH value less than 9 is used as a standard when the inorganic oxide solid electrolyte is dispersed in water, and the dispersion stability of the inorganic oxide solid electrolyte can be improved by matching the inorganic oxide solid electrolyte with a proton solvent.
In addition, the inorganic oxide solid electrolyte obtained by the traditional solid-phase method is difficult to form stably dispersed colloid in a solvent for hundred-nanometer-level particles after grinding and dispersing, and only suspension can be formed. The stability of the suspension is far worse than that of colloid, and the suspension can be settled quickly due to the gravity action of particles, so that the realization difficulty is high. In the prior art, an inorganic oxide solid electrolyte is dispersed in a solvent to obtain a dispersion system, and the dispersion system is used in the production of lithium batteries. However, the solid electrolyte dispersion system used by the lithium battery has the disadvantages that the system is complicated due to the addition of additives such as dispersing agents, and the like, and the composition and the battery performance of the lithium battery are adversely affected; or the control system is low in solid content and a somewhat stable dispersion system over a period of time is obtained by a complex process. Such low solids dispersions typically have solids levels below 20% by weight, lower solids levels can result in low system concentrations, are detrimental to control of the dosage and the addition of more solvent to the lithium battery production slurry can severely affect the slurry concentration and adversely affect subsequent lithium battery production. Meanwhile, the currently known dispersing agent-free low-solid-content dispersion liquid system cannot exist stably for a long time, and when the dispersion liquid system is placed for a long time (more than or equal to 20 days), sedimentation layering phenomenon of the solid electrolyte can occur, and adverse effects on the use of materials can be generated.
Meanwhile, the inorganic oxide solid electrolyte dispersion liquid can face the sedimentation problem caused by long-time standing when being stored and transported. During storage, the inorganic oxide solid electrolyte particles gradually sink to the vertical direction under the action of gravity, and are solidified to form hard blocks which cannot be dispersed again when standing for a long time. Meanwhile, the unstable solid content can lead to different solid contents at various positions in a dispersion liquid system, and the non-uniformity of the dispersion liquid can seriously influence the precision in material use and finally influence the consistency of a finished product. During the production process, the dispersion liquid sedimentation can cause electrolyte to remain in slurry circulation areas such as pipelines of a slurry mixing device, and deposit slowly with time, and formed caking can block the pipelines, so that the production device is damaged.
The problem of stability of the solid content of the dispersion liquid can be solved by means of particle size reduction, centrifugal treatment, dispersant addition, ultrasonic dispersion and the like.
Reducing the particle size can change the suspension into a dispersion with colloidal properties, and remain stable against sedimentation. The problem with this approach is that it is very difficult to make the particle size small, and as the particle radius decreases, the energy required for crushing increases exponentially, and the processing difficulty is high.
In addition to reducing the particle size, centrifugal processes have also been used to obtain dispersions with low solids content and small particle size to maintain a stable solids content, but such processes typically result in dispersions with solids contents of less than 5%. This results in the need to transfer a large amount of solvent during transportation, a significant increase in the cost of transportation of the dispersion, and an increase in the cost and safety risk.
Patent CN113540688A describes a preparation method and application of a separator coating material. The LATP, the Li-Al double metal hydroxide and the binder are dispersed in a solvent to obtain a dispersion liquid, and finally the dispersion liquid is uniformly coated on the diaphragm by porous extrusion to obtain the coating material. LATP particles are selected to be 300-900nm, the solvent is organic solvent NMP, polyvinyl alcohol is used as a dispersing agent, and dispersion liquid with the solid content of 20-37% is obtained. The method introduces a special dispersing agent, but affects the purity of the system, and even if the dispersing agent is added, the dispersion liquid cannot be stably agglomerated or settled for a long time.
Patent CN114073946a describes a graphene oxide/titanium dioxide composite nanomaterial, and a preparation method and application thereof, and the method is to obtain a composite material with good dispersibility and long-term stability by stirring and ultrasonic dispersion of graphene oxide and polymer coated titanium dioxide nanoparticles in water or ethanol solution respectively, and then mixing and stirring. However, the method requires titanium dioxide particles of 5-100 nm, and the solid content of the dispersion liquid is 0.01-0.1%, so that the production cost is increased, and the large-scale production is not easy to realize. The ultrasonic process can only play a role in dispersing, the ultrasonic process cannot play a role in crushing large-particle solid electrolyte, and the ultrasonic process is difficult to amplify, so that generated sound waves have great harm to the environment and human bodies.
Patent CN201810560205.3 describes a method for preparing a stable dispersion of solid content by combining a dispersant with a low temperature centrifugation technique. The method has the advantages that the phenomenon of gradient distribution of solid content occurs in the centrifugation process, the solid content of the dispersion liquid is not uniform, the control of the effective component weight during the blending of electrolyte slurry is not facilitated, and the dispersing agent is introduced, so that the system is selective, and the overall purity is influenced.
In view of the above findings, it is widely believed that the method for improving the stability of the dispersion of the inorganic oxide solid electrolyte material is mainly based on the use of additives and the reduction of the solid content. However, the methods are difficult to simultaneously have the requirements of simple operation, no impurity introduction, long-term stability, expanded production and cost saving.
The invention comprises the following steps:
the invention provides an inorganic oxide solid electrolyte dispersion liquid with stable solid content and a preparation method thereof, aiming at the problems existing in the prior art. The dispersion liquid adopts a proton type solvent, and selects an inorganic oxide solid electrolyte with weak lithium ion dissociation capability, does not use a dispersing agent, has high solid content, can keep the solid content at each position of the dispersion liquid stable when standing for a long time, does not agglomerate dispersed particles, can be directly used without ultrasonic dispersion treatment, reduces the use amount of the solvent, and reduces the preparation and transportation cost.
The inorganic oxide solid electrolyte dispersion liquid consists of inorganic oxide solid electrolyte and a solvent, and is free of additives;
the solvent is a protic solvent;
the solid content of the dispersion liquid is 25% -85%;
the solid content stability means that the solid content change value of the dispersion liquid after standing for 30 days is less than 2%.
The inorganic oxide solid electrolyte dispersion liquid is characterized in that:
the inorganic oxide solid electrolyte is NASICON type electrolyte, liSICON type electrolyte, and 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 0.7,0, x2 is more than or equal to 0 and less than or equal to 2 and less than 1, x3 is more than or equal to 0 and less than or equal to 1, and y is more than 0 and less than 0.1.
The inorganic oxide solid electrolyte is preferably 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 1+ x5 Zr 2 Si x5 P 3-x5 O 12 、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 And Na-beta/beta "-Al 2 O 3 Wherein 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.ltoreq.x1.ltoreq. 0.7,0 < x2 < 1,0 < x3 < 1,0 < x4 < 0.6,0 < x5 < 3,0 < y < 0.1,0 < n < 3;
more preferably, the inorganic oxide solid electrolyte is Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 、Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 、LiTiOPO 4 、LiHAl(PO 4 ) 0.96 F 0.08 At least one of them.
Preferably, the proton solvent comprises at least one of deionized water, ethanol, ethylene glycol, isopropanol and acetonitrile.
The solid content of the inorganic oxide solid electrolyte dispersion is related to the particle size of the inorganic solid electrolyte in the dispersion;
when the particle size of the inorganic oxide solid electrolyte is 10nm-300nm, the solid content of the dispersion liquid is 25% -70%; when the particle size of the inorganic oxide solid electrolyte is 300nm-2 μm, the solid content of the dispersion is 35% -85%.
Preferably, the solid content of the inorganic oxide solid electrolyte in the dispersion liquid is 25% -70% when the particle size of the inorganic oxide solid electrolyte in the dispersion liquid is 50nm-300nm, and the solid content of the inorganic oxide solid electrolyte in the dispersion liquid is 35% -85% when the particle size of the inorganic oxide solid electrolyte in the dispersion liquid is 300nm-1 μm.
After the dispersion is stood for 30 days, the particle size change value is less than 5%.
The invention also provides a preparation method of the inorganic oxide solid electrolyte dispersion liquid, which specifically comprises the following steps:
1) Mixing: grinding media, inorganic oxide solid electrolyte powder, and solvent are added to the grinding chamber.
2) Grinding; grinding the mixed grinding medium, inorganic oxide solid electrolyte powder and solvent in the grinding cavity.
Preferably, the particle size of the inorganic oxide solid electrolyte powder in the step 1) is 0.1 to 100 μm.
Preferably, in the step 1), the mass ratio of the grinding medium, the inorganic oxide solid electrolyte and the solvent is (1-20): 1: (0.17-4).
Preferably, the grinding medium adopts 0.1-10 mm grinding beads, the grinding linear speed in the step 2) is 4-20 m/s, and the grinding time is 0.5-72 h.
The application of the inorganic oxide solid electrolyte dispersion liquid in lithium batteries comprises application to liquid batteries and solid batteries.
The application method comprises the steps of directly applying or diluting, and then applying to the surface coating of the negative electrode, the surface coating of the negative electrode particles and the coating of the separator.
According to the invention, the inorganic oxide solid electrolyte with strong Li-H exchange capability presents strong alkalinity in water according to the pH value of the inorganic oxide solid electrolyte in water as a screening basis, and the solvent promotes the occurrence of the surface exchange process of the inorganic oxide solid electrolyte when dispersed in a proton solvent, so that the charge state of the particle surface is changed, the charge of the particle surface of the inorganic oxide solid electrolyte is changed, and the particles tend to be agglomerated rather than dispersed. For inorganic oxide solid electrolyte with pH less than 9 when dispersed in water, li-H exchange capability is weak, the influence of proton solvent is small, and the electrolyte can be kept stable in solution by means of hydrogen bond, electrostatic force and Van der Waals force.
The solid content stable dispersion liquid prepared by the invention has certain fluidity in the preparation process and after the preparation, the viscosity of the dispersion liquid is gradually increased along with the increase of the standing time, the solid content of the system is maintained to be almost unchanged from the solid content of the system after the preparation, and the inorganic oxide solid electrolyte particles cannot be settled in the standing process. The principle is as follows: because of the high solids content of the dispersion, most of the solvent is bound by the inorganic particles by electrostatic-dipole forces, becoming bound solvents, and only a small portion of the solvent is free, providing fluidity. In the ball milling and crushing process, particles in the dispersion liquid collide with ball milling beads to provide energy, so that part of the combined solvent becomes free solvent, and the dispersion liquid has certain fluidity and meets the processing requirement. When the ball milling process is finished and the dispersion is kept still, the free solvent is gradually attracted by the inorganic particles to become a combined solvent, the fluidity of the dispersion is reduced, the viscosity is increased, and the inorganic particles are prevented from settling in the dispersion. This phenomenon is not likely to occur at low solids contents because at high free solvent ratios, the action of the solute-bound solvent cannot significantly increase the slurry viscosity, ultimately leading to particle settling. In practical use, the solid content can be improved to prevent long-time standing settlement.
Compared with the prior art, the invention has the beneficial effects that;
1. according to the invention, the inorganic oxide solid electrolyte dispersion liquid is prepared by matching the proton solvent and the inorganic oxide solid electrolyte with weak lithium ion dissociation capability, so that particles are not easy to agglomerate, the particle size stability is high, the method can be used for coating the surface of a negative electrode plate, the infiltration effect of a solid electrolyte coating and a negative electrode is improved, and the safety performance of the negative electrode is improved.
2. According to the preparation method of the electrolyte dispersion liquid with stable solid content, the obtained dispersion liquid has excellent solid content stability by improving the solid content of the dispersion liquid, sedimentation and agglomeration are not generated in the actual production, and the problems of uneven dispersion liquid caused by sedimentation and agglomeration of the dispersion liquid during transportation and effective solid sedimentation during feeding and pipeline blockage caused by sedimentation and agglomeration of the suspension liquid during pipeline retention are effectively prevented.
3. The invention does not need to use additives, improves the purity of the system, and reduces the selectivity to solvents and dispersion materials
4. The invention improves the solid content of the dispersion liquid, reduces the solvent consumption and reduces the cost.
5. The invention improves the component proportion in the method for preparing the dispersion liquid by grinding, and has simple preparation method and easy scale-up production.
Detailed Description
The present invention will now be described in more detail with reference to the following examples, which are given by way of illustration only and are not to be construed as limiting the scope of the invention, as many insubstantial modifications and adaptations of the invention using its teachings will be within the scope of the invention.
The method for testing the stability of the solid content of the dispersion liquid comprises the following steps:
the solid content of the dispersion was tested using a drying method, and the solid content stability test steps were as follows:
1. the prepared dispersion was taken for testing the solids content and recorded as the initial solids content.
2. 100ml of the dispersion was placed in a 150ml flask, and the flask was sealed and left to stand for 30 days. After 30 days, 1ml of the dispersion was taken from the flask at a distance of 5mm from the liquid surface, and the solid content was measured and recorded as the upper solid content w1 of the dispersion. 1ml of the dispersion liquid in the experimental bottle at a position 5mm away from the bottle bottom is taken, and the solid content is tested and recorded as the lower solid content w2 of the dispersion liquid.
3. The dispersion stability S was measured by the deviation of the upper and lower layer solids w1 and w2 from the initial solids w 0. Wherein, the upper layer solid content change value is S1= |w1-w0|/w0×100%, and the lower layer solid content change value is S2= |w2-w0|/w0×100%; the smaller the values of S1 and S2, the more stable the slurry.
The particle size stability test method of the dispersion liquid comprises the following steps:
the particle size of the dispersion was measured using a nanoparticle sizer, the solvent used was consistent with the dispersion solvent, and the particle size stability was measured as follows:
1. the prepared dispersion was tested for solids content and recorded as the initial average particle size D0.
2. 100ml of the dispersion was placed in a 150ml flask, and the flask was sealed and left to stand for 30 days. After 30 days, 1ml of the dispersion was taken from the flask at a distance of 5mm from the liquid surface, and the solid content was measured and recorded as the upper layer particle size D1 of the dispersion. 1ml of the dispersion liquid in the experimental bottle at a position 5mm away from the bottle bottom is taken, the solid content is tested, and the solid content is recorded as a lower layer particle size value D2 of the dispersion liquid.
3. The dispersion particle size stability T is measured by using the deviation of the upper and lower particle size values D1 and D2 from the initial particle size value D0. Wherein the size change value of the upper layer particles of the slurry is T1= |D1-D0|/D0 multiplied by 100%, and the size change value of the lower layer particles is T2= |D2-D0|/D0 multiplied by 100%; the smaller the values of T1 and T2, the more stable the dispersion particle size.
Examples example 1:
step one: 100 parts by weight of Li having a particle diameter of 200nm 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Adding 500 parts by weight of powder, 300 parts by weight of 0.1mm zirconium balls and deionized water into the grinding cavity, and uniformly stirring. Therein 1gLi 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Ph=6.45 when dispersed in 10mL of water;
step two: zirconium balls and Li mixed in grinding cavity by sand mill 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Grinding the powder and deionized water to obtain dispersion slurry with the solid content of 25.15wt%, wherein d50=10 nm, the grinding time is 7 hours, and the grinding linear velocity=20m/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.
Examples example 2:
step one: 100 parts by weight of Li having a particle diameter of 3 μm 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Adding the powder, 500 parts by weight of a 2mm zirconium ball and 185 parts by weight of deionized water into a grinding cavity, and uniformly stirring. Therein 1gLi 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Ph=6.45 when dispersed in 10mL of water;
step two: zirconium balls and Li mixed in the grinding chamber by using a ball mill 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 The powder was milled with deionized water to a dispersion slurry with a solids content of 35.15wt%, d50=190 nm for 16 hours at a milling line speed=10 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.
Example 3:
step one: 100 parts by weight of Li having a particle diameter of 3 μm 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Adding the powder, 500 parts by weight of 2mm zirconium balls and 43 parts by weight of deionized water into a grinding cavity, and uniformly stirring. Therein 1gLi 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Ph=6.45 when dispersed in 10mL of water;
step two: zirconium balls and Li mixed in the grinding chamber by using a ball mill 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 The powder was milled with deionized water to a dispersion slurry with a solids content of 68.95wt%, d50=298 nm for 12 hours with a milling line speed=10 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.
Example 4:
step one: 100 parts by weight of Li having a particle diameter of 3 μm 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Powder, 500 parts by weight of 0.6mm zirconium balls and 185 parts by weight of deionized water are added into the grinding cavity and stirred uniformly. Therein 1gLi 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Ph=6.45 when dispersed in 10mL of water;
step two: zirconium balls and Li mixed in grinding cavity by sand mill 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 The powder was milled with deionized water to a dispersion slurry with a solids content of 35.11wt%, d50=310 nm for a milling time of 2 hours with a milling line speed=20 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.
Example 5:
step one: 100 parts by weight of Li having a particle diameter of 3 μm 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Adding the powder, 500 parts by weight of 2mm zirconium balls and 18 parts by weight of deionized water into a grinding cavity, and uniformly stirring. Therein 1gLi 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Ph=6.45 when dispersed in 10mL of water;
step two: zirconium balls and Li mixed in the grinding chamber by using a ball mill 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 The powder was milled with deionized water to a dispersion slurry with a solids content of 84.34wt%, d50=1910 nm for a milling time of 3 hours with a milling line speed=10 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.
Example 6:
step one: 100 parts by weight of Li having a particle diameter of 3 μm 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Adding the powder, 500 parts by weight of 2mm zirconium balls and 42 parts by weight of deionized water into a grinding cavity, and uniformly stirring. Therein 1gLi 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Ph=6.45 when dispersed in 10mL of water;
step two: zirconium balls and Li mixed in the grinding chamber by using a ball mill 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 The powder was milled with deionized water to a dispersion slurry with a solids content of 70.88wt%, d50=413 nm for a milling time of 8 hours with a milling line speed=10 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.
Example 7:
step one: 100 weight of the mixture with a particle size of 3 μmParts by weight Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Adding the powder, 500 parts by weight of 2mm zirconium balls and 100 parts by weight of ethanol into a grinding cavity, and uniformly stirring. Therein 1gLi 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Ph=6.45 when dispersed in 10mL of water;
step two: zirconium balls and Li mixed in the grinding chamber by using a ball mill 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 The powder was milled with ethanol to a dispersion slurry with a solids content of 49.56wt%, d50=320 nm, for a milling time of 12 hours, at a milling line speed=10 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.
Example 8:
step one: 100 parts by weight of Li having a particle diameter of 3 μm 1.4 Al 0.4 Ge 1.6 (PO 4 ) 3 Adding the powder, 500 parts by weight of 2mm zirconium balls and 100 parts by weight of ethylene glycol into a grinding cavity, and uniformly stirring. Therein 1gLi 1.4 Al 0.4 Ge 1.6 (PO 4 ) 3 Ph=6.85 when dispersed in 10mL of water;
step two: zirconium balls and Li mixed in the grinding chamber by using a ball mill 1.4 Al 0.4 Ge 1.6 (PO 4 ) 3 The powder and ethylene glycol were milled to a dispersion slurry with a solids content of 50.15wt%, d50=356 nm, for a milling time of 8 hours, with a milling line speed=10 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.
Example 9:
step one: 100 parts by weight of LiHAl (PO) 4 ) 0.96 F 0.08 Adding 500 parts by weight of powder, 500 parts by weight of 0.6mm zirconium balls and 90 parts by weight of deionized water into the grinding cavity, and uniformly stirring. Wherein 1g LiHAl (PO 4 ) 0.96 F 0.08 Ph=8.04 when dispersed in 10mL of water;
step two: zirconium balls, liHAl (PO) mixed in the grinding chamber using a sand mill 4 ) 0.96 F 0.08 The powder was milled with deionized water to a dispersion slurry with a solids content of 53.13wt%, d50=403 nm for a milling time of 1 hour with a milling line speed=20 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.
Example 10:
step one: 100 parts by weight of LiHAl (PO) 4 ) 0.96 F 0.08 Adding the powder, 500 parts by weight of 2mm zirconium balls and 100 parts by weight of ethanol into a grinding cavity, and uniformly stirring. Wherein 1g LiHAl (PO 4 ) 0.96 F 0.08 Ph=8.04 when dispersed in 10mL of water;
step two: zirconium balls, liHAl (PO) mixed in the grinding chamber were mixed by using a ball mill 4 ) 0.96 F 0.08 The powder was milled with ethanol to a dispersion slurry with a solids content of 50.55wt%, d50=319 nm for a milling time of 12 hours with a milling line speed=10 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.
Example 11:
step one: 100 parts by weight of LiHAl (PO) 4 ) 0.96 F 0.08 Adding the powder, 500 parts by weight of 2mm zirconium balls and 100 parts by weight of ethylene glycol into a grinding cavity, and uniformly stirring. Wherein 1g LiHAl (PO 4 ) 0.96 F 0.08 Ph=8.04 when dispersed in 10mL of water;
step two: zirconium balls, liHAl (PO) mixed in the grinding chamber were mixed by a roller ball mill 4 ) 0.96 F 0.08 The powder and ethylene glycol were milled to a dispersion slurry with a solids content of 50.87wt%, d50=389 nm for 24 hours at a milling line speed=6 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.
Example 12:
step one: 100 parts by weight of LiTiOPO having a particle diameter of 3 μm 4 Adding 500 parts by weight of powder, 500 parts by weight of 0.6mm zirconium balls and 100 parts by weight of deionized water into the grinding cavity, and uniformly stirring. Wherein 1g of LiTiOPO 4 Ph=8.69 when dispersed in 10mL of water;
step two: zirconium balls and LiTiOPO mixed in the grinding chamber by using a sand machine 4 The powder was milled with deionized water to a dispersion slurry with a solids content of 50.89wt%, d50=335 nm for a milling time of 2 hours with a milling line speed=20 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.
Example 13:
step one: 100 parts by weight of LiTiOPO having a particle diameter of 3 μm 4 Powder, 500 weight portions of zirconium balls, 100 weight portions of ethanol are added into a grinding cavity and stirred uniformly. Wherein 1g of LiTiOPO 4 Ph=8.69 when dispersed in 10mL of water;
step two: zirconium balls, liTiOPO mixed in the grinding chamber were mixed by using a ball mill 4 The powder was milled with ethanol to a dispersion slurry with a solids content of 50.68wt%, d50=458 nm, for a milling time of 6 hours, at a milling line speed=10 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.
Comparative example 1:
step one: 100 parts by weight of Li having a particle diameter of 3 μm 3 La 0.67 TiO 3 Adding 500 parts by weight of powder, 500 parts by weight of 0.6mm zirconium balls and 150 parts by weight of deionized water into the grinding cavity, and uniformly stirring. Therein 1gLi 3 La 0.67 TiO 3 Ph=11.89 when dispersed in 10mL of water;
step two: zirconium balls and Li mixed in grinding cavity by sand mill 3 La 0.67 TiO 3 Powder and deionized waterGrinding to a dispersion slurry with a solids content of 40.35wt%, d50=2214 nm, for a grinding time of 3 hours, a grinding linear velocity=20m/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.
Comparative example 2:
step one: 100 parts by weight of Li having a particle diameter of 3 μm 7 La 3 Zr 2 O 12 Adding 500 parts by weight of powder, 500 parts by weight of 0.6mm zirconium balls and 150 parts by weight of deionized water into the grinding cavity, and uniformly stirring. Therein 1gLi 7 La 3 Zr 2 O 12 Ph=13.15 when dispersed in 10mL of water;
step two: zirconium balls and Li mixed in grinding cavity by sand mill 7 La 3 Zr 2 O 12 The powder was milled with deionized water to a dispersion slurry with a solids content of 40.58wt%, d50=2568 nm for a milling time of 3 hours with a milling line speed=20 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.
Comparative example 3:
step one: 100 parts by weight of LiTiOPO having a particle diameter of 3 μm 4 Adding the powder, 500 parts by weight of 2mm zirconium balls and 100 parts by weight of deionized water into a grinding cavity, and uniformly stirring. Wherein 1g of LiTiOPO 4 Ph=8.69 when dispersed in 10mL of water;
step two: zirconium balls, liTiOPO mixed in the grinding chamber were mixed by using a ball mill 4 The powder was milled with deionized water to a dispersion slurry with a solids content of 50.26wt%, d50=2868 nm for a milling time of 1 hour with a milling line speed=10 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.
Comparative example 4:
step one: 100 parts by weight of Li having a particle diameter of 3 μm 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Adding the powder, 500 parts by weight of 2mm zirconium balls and 400 parts by weight of ethanol into a grinding cavity, and uniformly stirring. Therein 1gLi 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Ph=6.45 when dispersed in 10mL of water;
step two: zirconium balls and Li mixed in the grinding chamber by using a ball mill 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 The powder was milled with ethanol to a dispersion slurry with a solids content of 20.22wt%, d50=318 nm for a milling time of 12 hours at a milling line speed=10 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.
Comparative example 5:
step one: 100 parts by weight of Li having a particle diameter of 3 μm 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Adding the powder, 500 parts by weight of 2mm zirconium balls and 100 parts by weight of normal hexane into a grinding cavity, and uniformly stirring. Therein 1gLi 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Ph=6.45 when dispersed in 10mL of water;
step two: zirconium balls and Li mixed in the grinding chamber by using a ball mill 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 The powder and n-hexane were milled to a dispersion slurry with a solids content of 48.52wt%, d50=2653 nm for a milling time of 16 hours with a milling line speed=10 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.
Comparative example 6:
step one: 100 parts by weight of Li having a particle diameter of 3 μm 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Powder, 500 parts by weight of 2mm zirconium balls, 230 parts by weight of water and 1 part by weight of dispersant PVDF are added into a grinding cavity and stirred uniformly. Therein 1gLi 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 Ph=6.45 when dispersed in 10mL of water;
step two: zirconium balls and Li mixed in the grinding chamber by using a ball mill 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 The powder, water and dispersant PVDF were milled to a dispersion slurry with a solids content of 30.22wt%, d50=411 nm for 8 hours at a milling line speed=10 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.
Comparative example 7:
step one: 100 parts by weight of LiHAl (PO) 4 ) 0.96 F 0.08 Adding the powder and 100 parts by weight of water into a centrifugal cavity, and uniformly stirring. Wherein 1g LiHAl (PO 4 ) 0.96 F 0.08 Ph=8.04 when dispersed in 10mL of water;
step two: liHAl (PO) will be mixed in the milling chamber using a centrifuge 4 ) 0.96 F 0.08 The powder was centrifuged with water to obtain a dispersion slurry having a solids content of 5.22wt% in the upper part and d50=102 nm, and the centrifugation time was 0.5 hours, and the centrifugation linear velocity=50 m/s.
Step three: and (3) uniformly dispersing the dispersion liquid obtained in the step two by ultrasonic.
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.
TABLE 1 results of stability test of the solid content of the dispersion
| Sequence number | W0/％ | W1/％ | W2/％ | S1 | S2 |
| Example 1 | 25.15 | 24.71 | 25.61 | 1.75％ | 1.83％ |
| Example 2 | 35.15 | 34.81 | 35.41 | 0.97％ | 0.74％ |
| Example 3 | 68.95 | 68.63 | 69.22 | 0.46％ | 0.39％ |
| Example 4 | 35.11 | 34.45 | 35.78 | 1.88％ | 1.91％ |
| Example 5 | 84.34 | 82.81 | 85.78 | 1.81％ | 1.71％ |
| Example 6 | 70.88 | 70.11 | 71.85 | 1.09％ | 1.37％ |
| Example 7 | 49.56 | 49.11 | 50.02 | 0.91％ | 0.93％ |
| Example 8 | 50.15 | 49.31 | 50.92 | 1.67％ | 1.54％ |
| Example 9 | 53.13 | 52.24 | 53.98 | 1.68％ | 1.60％ |
| Example 10 | 50.55 | 50.02 | 51.46 | 1.05％ | 1.80％ |
| Example 11 | 50.87 | 50.27 | 50.08 | 1.18％ | 1.55％ |
| Example 12 | 50.89 | 50.12 | 51.74 | 1.51％ | 1.67％ |
| Example 13 | 50.68 | 50.23 | 50.14 | 0.89％ | 1.07％ |
| Comparative example 1 | 40.35 | 33.56 | 48.88 | 16.83％ | 21.14％ |
| Comparative example 2 | 40.58 | 34.78 | 48.99 | 14.29％ | 20.72％ |
| Comparative example 3 | 50.26 | 40.58 | 60.88 | 19.26％ | 21.13％ |
| Comparative example 4 | 20.22 | 18.22 | 22.68 | 9.89％ | 12.17％ |
| Comparative example 5 | 48.52 | 5.32 | 80.35 | 89.04％ | 65.60％ |
| Comparative example 6 | 30.22 | 27.22 | 33.68 | 9.93％ | 11.45％ |
| Comparative example 7 | 5.22 | 2.22 | 7.68 | 57.47％ | 47.13％ |
TABLE 2 particle size stability test results of the dispersions
As can be seen from the examples, the dispersion of the present invention has excellent solid content stability and particle size stability. After standing for 30 days, the solid content change rate of the upper layer and the lower layer is less than 2%, and the granularity change rate is less than 5%. From examples 2 and 4, 3 and 6, it can be seen that the slurry solid content stability increases with decreasing particle size when the electrolyte material and the dispersion solvent are the same, and from examples 3 and 4, it can be seen that the slurry solid content stability increases with increasing solid content. As is clear from comparative examples 1 and 2, the inorganic oxide solid electrolyte material having a high pH in water is easily aggregated in a proton solvent, and it is impossible to prevent sedimentation by increasing the solid content. From example 12 and comparative example 3, it is seen that it is difficult for large particles having a particle diameter of more than 2 μm to improve the stability of the solid content by increasing the solid content because the interaction of the large particles with the solvent is too weak and is more affected by gravity. From example 6 and comparative example 4, it is seen that the slurry stability is significantly reduced after the solid content is reduced. It can be seen from comparative example 5 that no interaction with the solid electrolyte particles was observed in the aprotic solvent, and even the increase in the solid content did not allow uniform dispersion. As can be seen from comparative example 6, the method of improving the stability of the solid content by adding the dispersant at a low solid content is not ideal, and it is also related to the choice of dispersant. From comparative example 7, it can be seen that the low solids small particle size dispersion obtained by centrifugation still does not completely avoid the problem of sedimentation after standing for a long period of time.
The prepared dispersion liquid is mixed in the negative electrode, or coated on the surface of the negative electrode plate, or coated on the surface of the negative electrode material, so that the electrical property and the safety performance of the battery can be improved.
It is to be understood that the above embodiments are merely illustrative of the application of the principles of the present invention, but not in limitation thereof. Various modifications and improvements may be made by those skilled in the art without departing from the spirit and substance of the invention, and such modifications are also considered to be within the scope of the invention.
Claims (10)
1. An inorganic oxide solid electrolyte dispersion having a stable solid content, characterized in that:
the inorganic oxide solid electrolyte dispersion liquid consists of inorganic oxide solid electrolyte and a solvent, and is free of additives;
the solvent is a protic solvent;
the solid content of the dispersion liquid is 25% -85%;
the solid content stability means that the solid content change value of the dispersion liquid after standing for 30 days is less than 2%.
2. The inorganic oxide solid state electrolyte dispersion according to claim 1, characterized in that:
the inorganic oxide solid electrolyte is selected from NASICON type electrolyte, liSIICON type electrolyte and 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 And Na-beta/beta "-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 0.7,0, x2 is more than or equal to 0 and less than or equal to 2 and less than 1, x3 is more than or equal to 0 and less than or equal to 1, and y is more than 0 and less than 0.1.
3. The inorganic oxide solid state electrolyte dispersion according to claim 1, characterized in that:
the inorganic oxide solid electrolyte is selected from 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 1+x5 Zr 2 Si x5 P 3-x5 O 12 、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 And Na-beta/beta "-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 0.7,0 and less than or equal to x2 and less than or equal to 0 and less than or equal to 1, x3 and less than or equal to 0 and less than 1, x4 and less than or equal to 0 and less than or equal to 0.6,0 and less than or equal to 5 and less than 3, y and less than 0 and less than or equal to 0.1, and n and less than 3.
4. The inorganic oxide solid state electrolyte dispersion according to claim 1, characterized in that:
the inorganic oxide solid electrolyte is selected from Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 、Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 、LiTiOPO 4 And LiHAl (PO) 4 ) 0.96 F 0.08 At least one of them.
5. The inorganic oxide solid state electrolyte dispersion according to claim 1, characterized in that:
the proton solvent is at least one selected from deionized water, ethanol, ethylene glycol and isopropanol.
6. The inorganic oxide solid state electrolyte dispersion according to claim 1, characterized in that:
the solid content of the inorganic oxide solid electrolyte dispersion is related to the particle size of the inorganic solid electrolyte in the dispersion;
when the particle size of the inorganic oxide solid electrolyte is 10nm-300nm, the solid content of the dispersion liquid is 25% -70%;
when the particle size of the inorganic oxide solid electrolyte is 300nm-2 μm, the solid content of the dispersion is 35% -85%.
7. A method for preparing the inorganic oxide solid electrolyte dispersion of claim 1, characterized in that:
mixing and grinding the inorganic oxide solid electrolyte and the solvent to form a dispersion liquid, and specifically comprises the following steps:
1) Mixing: adding grinding medium, inorganic oxide solid electrolyte powder and solvent into a grinding cavity, and stirring at a low speed to uniformly mix the materials;
2) Grinding: grinding the mixed grinding medium, inorganic oxide solid electrolyte powder and solvent in the grinding cavity.
8. The method for producing an inorganic oxide solid electrolyte dispersion according to claim 7, characterized in that:
the particle size of the inorganic oxide solid electrolyte powder in the step 1) is 0.1-100 mu m.
In the step 1), the mass ratio of the grinding medium, the inorganic oxide solid electrolyte powder and the solvent is (1-20) 1: (0.17-4).
9. The method for producing an inorganic oxide solid electrolyte dispersion according to claim 7, characterized in that:
the grinding medium is grinding beads with the thickness of 0.1-10 mm, the grinding linear speed in the step 2) is 4-20 m/s, and the grinding time is 0.5-72 h.
10. Use of the inorganic oxide solid state electrolyte dispersion of any one of claims 1-6 in a lithium battery, which is a liquid battery or a solid state battery.
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