CN220086124U - Solid electrolyte structure - Google Patents
Solid electrolyte structure Download PDFInfo
- Publication number
- CN220086124U CN220086124U CN202222007180.9U CN202222007180U CN220086124U CN 220086124 U CN220086124 U CN 220086124U CN 202222007180 U CN202222007180 U CN 202222007180U CN 220086124 U CN220086124 U CN 220086124U
- Authority
- CN
- China
- Prior art keywords
- solid electrolyte
- protective layer
- solid
- titanium
- electrolyte structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 84
- 239000010936 titanium Substances 0.000 claims abstract description 44
- 239000011241 protective layer Substances 0.000 claims abstract description 40
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 39
- 239000007787 solid Substances 0.000 claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 12
- 239000002184 metal Substances 0.000 claims abstract description 12
- 239000010410 layer Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 37
- 150000002500 ions Chemical class 0.000 claims description 21
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 12
- 239000003792 electrolyte Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical group [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 claims description 6
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 5
- 229920001328 Polyvinylidene chloride Polymers 0.000 claims description 5
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 5
- 239000005033 polyvinylidene chloride Substances 0.000 claims description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- DUSBUJMVTRZABV-UHFFFAOYSA-M [O-2].O[Nb+4].[O-2] Chemical compound [O-2].O[Nb+4].[O-2] DUSBUJMVTRZABV-UHFFFAOYSA-M 0.000 claims description 3
- 239000002608 ionic liquid Substances 0.000 claims description 3
- 229920000193 polymethacrylate Polymers 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 150000003839 salts Chemical group 0.000 claims description 3
- -1 dimethyl vinylidene Chemical group 0.000 claims 1
- 229920000620 organic polymer Polymers 0.000 abstract description 2
- 238000006276 transfer reaction Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 239000011244 liquid electrolyte Substances 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000011149 active material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910013553 LiNO Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 229910000484 niobium oxide Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 229910008731 Li2O-Al2O3-SiO2-P2O5-TiO2 Inorganic materials 0.000 description 1
- 229910008547 Li2O—Al2O3—SiO2—P2O5—TiO2 Inorganic materials 0.000 description 1
- 229910008550 Li2O—Al2O3—SiO2—P2O5—TiO2—GeO2 Inorganic materials 0.000 description 1
- XRNHBMJMFUBOID-UHFFFAOYSA-N [O].[Zr].[La].[Li] Chemical compound [O].[Zr].[La].[Li] XRNHBMJMFUBOID-UHFFFAOYSA-N 0.000 description 1
- PHDNGVHIVIYFJP-UHFFFAOYSA-N [Zr].[La].[Li] Chemical compound [Zr].[La].[Li] PHDNGVHIVIYFJP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
-
- 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
- H01M2300/0071—Oxides
-
- 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
- H01M2300/0082—Organic polymers
-
- 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
- H01M2300/0088—Composites
- H01M2300/0094—Composites in the form of layered products, e.g. coatings
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Primary Cells (AREA)
- Conductive Materials (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The utility model provides a solid electrolyte structure, which aims at the solid electrolyte containing titanium components, the surface of the solid electrolyte is completely coated with a titanium component precipitation-preventing protective layer, and the protective layer is prepared by solid oxidized metal or organic polymer, so that the reduction reaction of the titanium components under lower voltage can be effectively prevented, the pollution or influence of titanium on a polar layer can be effectively prevented, the chemical resistance of the titanium-containing solid electrolyte is improved, the application of the solid electrolyte containing titanium components is greatly increased, and meanwhile, the contact state of the solid electrolyte surface can be improved by matching with the arrangement of the protective layer, and various defects of small contact surface, poor contact surface, lower charge transfer reaction constant and the like of the solid electrolyte can be solved.
Description
Technical Field
The present utility model relates to a solid electrolyte structure, and more particularly to a titanium-containing solid electrolyte structure with a protective layer.
Background
The existing lithium ion secondary battery mainly uses liquid electrolyte as a lithium ion transmission medium, however, the volatile characteristic of the liquid electrolyte can cause adverse effects on human body and environment; meanwhile, the flammability of the liquid electrolyte is also a great safety concern for battery users.
Moreover, one of the reasons for the unstable performance of the lithium battery is mainly that the electrode has a relatively high surface activity (negative electrode) and a relatively high voltage (positive electrode), and the interface between the electrode and the electrolyte is unstable due to the direct contact, so that a so-called exothermic reaction is generated to form a passive protection film on the contact interface, and the liquid electrolyte and lithium ions are consumed by the reactions, and heat is also generated. Once a local short circuit occurs, the local temperature rises rapidly, and the passive protective film becomes unstable and releases heat; this exothermic reaction is cumulative, thus allowing the temperature of the battery as a whole to continue to rise. Once the battery temperature increases to the initial temperature (or trigger temperature) of the thermal runaway reaction, thermal runaway phenomenon is induced, and thus damage phenomenon of the battery, such as explosion or fire, is caused, which causes considerable safety concern in use.
In recent years, solid electrolytes have become another focus of research, which have ionic conductivity similar to that of liquid electrolytes, but do not have the properties of liquid electrolytes that are easily vaporized and burned, while the interface with the active material surface is relatively stable (whether chemical or electrochemical). However, unlike liquid electrolyte, solid electrolyte has small contact surface with active material, poor contact surface and low charge transfer reaction constant, so that the problem of high resistance of charge transfer interface with active material of positive and negative electrodes in the electrode layer is existed, which is unfavorable for effective transmission of lithium ions, so that it is still difficult to replace liquid electrolyte completely.
In addition, the cost of the solid electrolyte is also greatly increased compared with that of the liquid electrolyte, and various materials have been developed in recent years in order to reduce the cost and control the compatibility with the improved materials; among them, for example, lithium Aluminum Titanium Phosphate (LATP) solid electrolyte has a considerable cost advantage in addition to good ionic conductivity, however, lithium Aluminum Titanium Phosphate (LATP) solid electrolyte has poor low voltage electrochemical resistance because it contains titanium component, and when precipitated, it reacts with lithium (ions) to contaminate the anode layer, thereby affecting the normal performance of electrochemical reaction, so that it is difficult to expand its application range.
How to effectively and largely apply the solid electrolyte and simultaneously consider the cost and the improvement of the surface state of the solid electrolyte is a problem to be solved in the field.
Disclosure of Invention
In view of the above, the present utility model provides a solid electrolyte structure comprising: a titanium (Ti) -containing solid electrolyte particle; and a titanium component precipitation-preventing protective layer positioned on the surface of the titanium-containing solid electrolyte particles; wherein the protective layer completely coats the titanium-containing solid electrolyte particles, prevents the titanium component in the solid electrolyte particles from undergoing a reduction reaction, and improves the chemical resistance of the solid electrolyte particles; wherein the thickness of the titanium component precipitation preventing protective layer is 50-500 nanometers.
Preferably, the titanium (Ti) -containing solid electrolyte particles are Lithium Aluminum Titanium Phosphate (LATP) solid electrolyte particles. Preferably, the protective layer is a solid oxide protective layer, a polymeric protective layer, or a combination thereof.
Preferably, the solid oxide metal protective layer is formed from niobium trioxide (Nb 2 O 3 ) And derivatives thereof.
Preferably, the solid oxide metal protective layer is formed of lithium nitrate (LiNO x ) And derivatives thereof.
Preferably, the solid oxide metal protective layer is formed of a lithium lanthanum zirconium oxide solid electrolyte (lithium lanthanum zirconium oxide; li) 7 La 3 Zr 2 O 12 The method comprises the steps of carrying out a first treatment on the surface of the LLZO).
Preferably, the polymer type protection layer comprises an ion-conducting body.
Preferably, the ion conductive body is made of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), potassium Polymethacrylate (PMMA), or polyvinylidene chloride (PVC).
Preferably, a film forming agent is added to the ion-conductive body.
Preferably, the ion-conducting body is added with a shaping agent.
Preferably, the ion conducting body is an ionic liquid (ion liquid).
Preferably, the ion-conducting body includes an ion donor (ion donor material).
Preferably, the ion donor is a salt.
The main object of the present utility model is to provide a solid electrolyte structure, which can solve the above-mentioned drawbacks of the prior art, and which has low material cost and can be applied to each electrode layer without limitation. Another object of the present utility model is to provide a solid electrolyte structure, which can solve various problems such as high charge transfer resistance and low contact area caused by contact surface of solid electrolyte, besides preventing precipitation of internal titanium component by using the arrangement of the protective layer.
In order to achieve the above object, the present utility model provides a solid electrolyte structure capable of effectively preventing contamination of a polar layer with a titanium component, and expanding the application range of a titanium-containing solid electrolyte.
Wherein, the protective layer can be formed by solid oxidation metal, polymer type or the composition of the solid oxidation metal, and can effectively prevent the reduction of titanium components and improve the electrochemical resistance under low voltage for solid electrolyte particles; for the outside of the solid electrolyte particles, the problem of high charge transfer resistance and low contact area derivative generated by the contact interface of the solid electrolyte can be solved by arranging the protective layer, so that the optimal ion conduction mode can be achieved under the condition of considering the cost and the safety.
The objects, technical contents, features and effects achieved by the present utility model will be more easily understood by the following detailed description of the embodiments.
Drawings
Fig. 1 is a schematic view of a solid electrolyte structure provided in an embodiment of the present utility model.
Fig. 2 is a graph showing a titanium concentration distribution of a solid electrolyte structure according to an embodiment of the present utility model.
Reference numerals
10. Solid electrolyte structure
11. Solid electrolyte particles
12. Protective layer
Detailed Description
As shown in fig. 1, a schematic diagram of a solid electrolyte structure provided in an embodiment of the present utility model is shown. The solid electrolyte structure 10 disclosed in the present utility model is mainly composed of solid electrolyte particles 11 and a titanium component precipitation preventing protective layer 12, wherein the solid electrolyte particles 11 are solid electrolytes containing titanium (Ti) components, such as lithium aluminum titanium phosphate (LATP; li) 1+ x Al x Ti 2–x (PO 4 ) 3 ) Solid electrolytes, which have relatively high ionic conductivity, good chemical and thermal stability, and low raw materials and manufacturing costs, have received considerable attention in recent years; however, the chemical resistance is poor, when titanium component is precipitated (especially in low pressure state), the surface property is changed, and the ionic conductivity of the surface is reduced, meanwhile, the interface impedance is greatly increased because titanium reacts with lithium (ions), so that the property and efficiency of electrochemical reaction are greatly reduced.
Therefore, the protection layer 12 completely covers the solid electrolyte particles 11 to prevent titanium components in the solid electrolyte particles 11 from precipitating, the thickness of the protection layer 12 is 10-500 nm, and the protection layer completely covers the surfaces of the solid electrolyte particles 11, and it should be noted that the solid electrolyte particles 11 are shown only by way of illustration, and the shape of the solid electrolyte particles is not limited to be circular (sphere), other spheroids, flakes, pages, etc. and the utility model is applicable.
Meanwhile, since the solid electrolyte particles 11 still need to have a certain ionic conductivity and good chemical and thermal stability after coating the protective layer 12, the material can be selected from solid oxide metals, organic polymers or their combination, and the forming method can be sintering, infiltration, coating, etc., and the utility model is not limited to a specific process. The solid electrolyte particles 11 may be oxides of various titanium-containing components other than the above-mentioned Lithium Aluminum Titanium Phosphate (LATP) as solid electrolytes, for example Li 1+x+y (Al,Ga) x (Ti,Ge) 2-x Si y P 3-y O 12 Crystallization, wherein 0.ltoreq.x.ltoreq.1 and 0.ltoreq.y.ltoreq.1, li 2 O-Al 2 O 3 -SiO 2 -P 2 O 5 -TiO 2 、Li 2 O-Al 2 O 3 -SiO 2 -P 2 O 5 -TiO 2 -GeO 2 、Li 3x La 2/3x TiO 3 、Li 0.38 La 0.56 Ti 0.99 Al 0.01 O 3 、Li 0.34 LaTiO 2.94 。
Referring to fig. 2, after the solid electrolyte particles 11 have the protective layer 12 on the surface, it is obvious that the precipitation of the titanium component (typically, the precipitation in the ionic state) is completely limited and only occurs inside the solid electrolyte particles 11 due to the obstruction of the protective layer 12, so that the main function and purpose of the protective layer 12 for the solid electrolyte particles 11 is to prevent the titanium component from precipitating outside the solid electrolyte structure 10.
Specifically, when the protective layer 12 is a solid oxide metal protective layer, the thickness is preferably about 10-50 nanometers, which may be, for example, niobium oxide (NbO) x ) And derivatives thereof, such as niobium trioxide (Nb) 2 O3) or lithium nitrate (LiNO) x ) And derivatives thereof. Alternatively, the protective layer 12 may be a lithium lanthanum zirconium oxygen solid state electrolyte (lithium lanthanum zirconium oxide; li) 7 La 3 Zr 2 O 12 The method comprises the steps of carrying out a first treatment on the surface of the LLZO) and lithium lanthanum zirconium oxygen(LLZO) has relatively stable chemical resistance, and is excellent in ion conductivity, chemical stability and thermal stability, but the material and manufacturing cost thereof are relatively high, so that the formation of the protective layer 12 on the surface of the titanium-containing solid electrolyte particles 11 (such as LATP) by using the Lithium Lanthanum Zirconium Oxide (LLZO) can greatly reduce the cost, and the chemical resistance of the solid electrolyte structure 10 can be improved through the relatively stable interface of the Lithium Lanthanum Zirconium Oxide (LLZO) to greatly increase the application range.
When the protective layer 12 is a polymer type protective layer, the thickness is preferably about 20-500 nm, and it may be a polymer ion-conducting host or a polymer type solid electrolyte. For example, the polymer ion conductive body is made of polyethylene oxide (PEO), polyvinylidene fluoride (PVDF), polyacrylonitrile (PAN), potassium Polymethacrylate (PMMA), polyvinylidene chloride (PVC), etc., and is modified by adding a film forming agent (such as cross-linked film forming material) and a shaping agent, so as to further improve the film forming property. When the film former is added, the former may be optionally retained or removed (added only during molding and removed after molding). The shaping agent may be selected from Propylene Carbonate (PC), ethylene Carbonate (EC), dimethylformamide (DMF), and dimethyl sulfoxide (DMSO).
In another embodiment, the polymeric ion-conductive body is added with a film-forming agent (such as a cross-linked film-forming material) and an ionic liquid (ion liquid). The solid polymer electrolyte as the protective layer 12 can prevent titanium components of the solid electrolyte particles 11 from being separated out, and the solid electrolyte particles 11 are coated on the outer edges of the solid electrolyte particles 11 due to softer texture, so that the contact interface state between the solid electrolyte particles 11 or between the solid electrolyte particles 11 and an active material can be greatly improved, the problem of high charge transfer resistance and low contact area which are generated can be effectively solved, and an optimal ion conduction mode can be achieved under the condition of combining cost and safety.
In the embodiment of the polymer form protection layer 12, an ion-supplying material (ion donor material), such as a salt, may be added to increase the ion-conducting capability, and become a polymer-type solid electrolyte. Or a solid electrolyte comprising an ion-conductive body, a film former and an ion-donating material.
In summary, the solid electrolyte structure provided by the utility model utilizes the arrangement of the titanium component precipitation-preventing protective layer, so that the titanium component precipitation can be effectively prevented for the inside of solid electrolyte particles, and the chemical resistance is improved; the problem of high charge transfer resistance and low contact area of the solid electrolyte caused by contact interface can be solved by arranging the protective layer outside the solid electrolyte particles, so that the optimal ion conduction mode can be achieved under the condition of considering the cost and the safety.
The foregoing description is only of the preferred embodiments of the utility model and is not intended to limit the scope of the utility model. Various modifications and equivalent substitutions made according to the features of the claims of the present utility model should be included in the scope of the claims of the present utility model.
Claims (12)
1. A solid state electrolyte structure, the solid state electrolyte structure comprising:
a titanium-containing solid electrolyte particle; and
a titanium component precipitation-preventing protective layer positioned on the surface of the titanium-containing solid electrolyte particles;
wherein the protective layer completely coats the titanium-containing solid electrolyte particles, prevents the titanium component in the solid electrolyte particles from undergoing a reduction reaction, and improves the chemical resistance of the solid electrolyte particles;
wherein the thickness of the titanium component precipitation-preventing protective layer is 50-500 nanometers;
the titanium-containing solid electrolyte particles are lithium aluminum titanium phosphate solid electrolyte particles.
2. The solid state electrolyte structure of claim 1 wherein the protective layer is a solid state oxidized metal protective layer, a polymeric protective layer, or a combination thereof.
3. The solid electrolyte structure of claim 2 wherein the solid oxide metal protective layer is made of niobium trioxide and derivatives thereof.
4. The solid electrolyte structure of claim 2, wherein the solid oxide metal protective layer is made of lithium nitrate and derivatives thereof.
5. The solid electrolyte structure of claim 2, wherein the material of the solid oxide metal protection layer is lithium lanthanum zirconium oxide solid electrolyte.
6. The solid state electrolyte structure of claim 2 wherein the polymer type protective layer comprises an ion conductive body.
7. The solid electrolyte structure of claim 6 wherein the ion-conductive body is made of any one of polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile, potassium polymethacrylate, and polyvinylidene chloride.
8. The solid state electrolyte structure of claim 1 wherein the ion conducting body has a film forming agent therein.
9. The solid electrolyte structure of claim 8, wherein the ion-conductive body has a shaping agent therein, and the shaping agent is any one of propylene carbonate, ethylene carbonate, dimethylformamide, and dimethyl vinylidene.
10. The solid state electrolyte structure of claim 8 wherein the ion conducting body is an ionic liquid.
11. The solid state electrolyte structure of claim 8, 9 or 10 wherein the ion conducting body comprises an ion donor.
12. The solid state electrolyte structure of claim 11 wherein the ion donor is a salt.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW110132794A TWI786805B (en) | 2021-09-03 | 2021-09-03 | Solid state electrolyte structure |
| TW110132794 | 2021-09-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN220086124U true CN220086124U (en) | 2023-11-24 |
Family
ID=83806506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202222007180.9U Active CN220086124U (en) | 2021-09-03 | 2022-08-01 | Solid electrolyte structure |
Country Status (4)
| Country | Link |
|---|---|
| KR (1) | KR20230000522U (en) |
| CN (1) | CN220086124U (en) |
| DE (1) | DE202022103923U1 (en) |
| TW (1) | TWI786805B (en) |
-
2021
- 2021-09-03 TW TW110132794A patent/TWI786805B/en active
-
2022
- 2022-07-12 DE DE202022103923.2U patent/DE202022103923U1/en active Active
- 2022-07-28 KR KR2020220001834U patent/KR20230000522U/en unknown
- 2022-08-01 CN CN202222007180.9U patent/CN220086124U/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| KR20230000522U (en) | 2023-03-10 |
| TWI786805B (en) | 2022-12-11 |
| DE202022103923U1 (en) | 2022-10-10 |
| TW202312548A (en) | 2023-03-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11482759B2 (en) | Oxidation resistant separator for a battery | |
| JP4958484B2 (en) | Non-aqueous electrolyte battery and manufacturing method thereof | |
| JP6840396B2 (en) | Modified ceramic separator complex and its manufacturing method | |
| JP2007280911A5 (en) | ||
| KR20090007710A (en) | Nonaqueous electrolyte battery and method for manufacturing same | |
| BRPI0809722B1 (en) | Electrochemical Device | |
| KR20090087827A (en) | Method of manufacturing cathode active material | |
| CN110651385A (en) | Negative electrode active material and negative electrode for solid-state battery comprising same | |
| KR102082616B1 (en) | Composite ELECTRODE MATERIALS WITH IMPROVED STRUCTURE | |
| JP2011192634A (en) | Nonaqueous electrolyte secondary battery | |
| EP3531481B1 (en) | Composite electrode materials | |
| CN220086124U (en) | Solid electrolyte structure | |
| CN110165221B (en) | Electrode layer composite material | |
| CN106784682A (en) | A kind of preparation method of metal oxide coating spinelle type LiMn2O4 | |
| CN111146411B (en) | Electrode layer composite material with improved structure | |
| KR101735148B1 (en) | Cathode thin film, cathode and secondary battery comprising the same | |
| JP2024501305A (en) | Positive electrode active material composite, positive electrode for secondary batteries containing the same, and secondary battery containing the same | |
| CN114824459A (en) | Metallic lithium and solid electrolyte interface layer and preparation method | |
| KR20230026263A (en) | Positive electrode active material composite, positive electrode for secondary battery including the same, and secondary battery including the same | |
| KR20240000393A (en) | Dual Ceramic Coating materials including Two or More Types of Ceramics and Manufacturing Method Thereof | |
| Atanasoski et al. | High energy insertion cathodes | |
| Atanasoski et al. | HIGH ENERGY INSERTION CATHODES zyxwvutsrqp | |
| JPWO2020167881A5 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GR01 | Patent grant | ||
| GR01 | Patent grant |