CN110556571A - lithium titanate lanthanum composite material, preparation method thereof and lithium ion solid-state battery - Google Patents
lithium titanate lanthanum composite material, preparation method thereof and lithium ion solid-state battery Download PDFInfo
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- 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
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- H—ELECTRICITY
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Abstract
The invention relates to a lithium lanthanum titanate composite material, a preparation method thereof and a lithium ion solid-state battery, wherein the lithium lanthanum titanate composite material is formed by compounding Li 3 OX with an anti-calcium state ore structure and lithium lanthanum titanate with a calcium state ore structure, the Li 3 OX is distributed at a crystal boundary between lithium lanthanum titanate crystal grains and partially diffuses into the lithium lanthanum titanate crystal grains, the chemical formula of the lithium lanthanum titanate is Li 3x La 2/3-x TiO 3, X is more than 0 and less than 0.16, and in the Li 3 OX, X is halogen.
Description
Technical Field
The invention belongs to the field of solid electrolytes, and particularly relates to a lithium titanate lanthanum composite material, a preparation method thereof and a lithium ion solid battery.
Background
At present, commercial lithium ion batteries generally use organic liquid electrolytes which contain flammable and explosive organic electrolytes, and the potential safety hazard of the organic liquid electrolytes limits the wide application of the lithium ion batteries. The lithium ion battery prepared by using the inorganic solid electrolyte to replace a liquid electrolyte and a diaphragm not only simplifies the battery structure, but also can fundamentally solve the safety problem, and further improves the service temperature range and the storage life of the lithium ion battery.
The oxide solid electrolyte has excellent stability and good room temperature ionic conductivity in air, and among the numerous inorganic solid electrolytes found, the conductivity is closer to the commercial level of lanthanum titanate material (LLTO), which has the chemical formula of Li 3x La 2/3-x TiO 3 (0 < x < 0.16), and the grain conductivity has reached 10 -3 S/cm at room temperature, but the grain boundary conductivity is lower, resulting in that the total grain boundary conductivity of LLTO is not practical.
The patent with publication number CN101325094B discloses a lithium lanthanum titanate composite solid electrolyte material and a synthesis method thereof, wherein the composite solid electrolyte contains an amorphous nano-silicon oxide layer at the grain boundary between lithium lanthanum titanate grains. The lithium titanate lanthanum composite solid electrolyte has a certain improvement effect on the conductivity of a crystal boundary, but the overall improvement effect is limited.
Disclosure of Invention
The invention aims to provide a lithium titanate lanthanum composite material, so as to solve the problem of low total conductivity of the existing lithium titanate lanthanum composite solid electrolyte. The invention also provides a preparation method of the lithium titanate lanthanum composite material and a lithium ion solid-state battery based on the lithium titanate lanthanum composite material.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
A lithium lanthanum titanate composite material is formed by compounding Li 3 OX with an anti-calcium state ore structure and lithium lanthanum titanate with a calcium state ore structure, wherein Li 3 OX is distributed at a crystal boundary between lithium lanthanum titanate crystal grains and partially diffuses into the lithium lanthanum titanate crystal grains, the chemical formula of the lithium lanthanum titanate is Li 3x La 2/3-x TiO 3, X is more than 0 and less than 0.16, and in Li 3 OX, X is halogen.
the lithium lanthanum titanate composite material of the invention utilizes Li 3 OX with rich lithium phase and low melting point to supplement cations to LLTO, changes the disorder degree of carriers or cation vacancies in crystal grains, improves the ionic conductivity in the crystal grains, compensates the consumption of lithium ions carried in a space charge layer at the crystal grain boundary, and effectively improves the ionic conductivity of the crystal grain boundary.
In order to further improve the structural stability of the lanthanum lithium titanate composite material and improve the grain boundary conductance and the total conductance of the composite material, the mass ratio of Li 3 OX and Li 3x La 2/3-x TiO 3 in the lanthanum lithium titanate composite material is preferably m (1-m), wherein m is more than 0 and less than 0.1, and more preferably 0.01 and less than 0.1. the optimal composition of lanthanum lithium titanate is Li 0.35 La 0.55 O 3 or Li 0.5 La 0.5 TiO 3.
A preparation method of a lithium titanate lanthanum composite material comprises the following steps of ball-milling and mixing Li 3 OX with an anti-calcium state ore structure and lithium titanate lanthanum with a calcium state ore structure, pressing and sintering to obtain the lithium titanate lanthanum, wherein the chemical formula of the lithium titanate lanthanum is Li 3x La 2/3- x TiO 3, X is more than 0 and less than 0.16, and in the Li 3 OX, X is halogen.
According to the preparation method of the lithium titanate lanthanum composite material, Li 3 OX is adopted to modify Li 3x La 2/3-x TiO 3 crystal boundary, so that Li 3 OX is enriched at the crystal boundary and is partially diffused into the crystal grain.
In the lithium lanthanum titanate composite material, the mass ratio of Li 3 OX to Li 3x La 2/3-x TiO 3 is m (1-m), wherein m is more than 0 and less than 0.1, more preferably m is more than 0.01 and less than 0.1, Li 3x La 2/3-x TiO 3 and Li 3 OX with the mass ratio of m (1-m) can be respectively prepared according to chemical compositions, and then the lithium lanthanum titanate composite material can be conveniently prepared according to the method.
In order to optimize the sintering process, promote mass transfer and ensure the uniform and consistent quality of the sinter, the pressure intensity during pressing is preferably 5-30 MPa.
The sintering is carried out in a protective atmosphere, and the protective atmosphere can adopt inert atmosphere such as argon and the like. In order to further ensure the stability of the sintering process and optimize the quality of the sintered body, the sintering temperature is 400-1250 ℃, and the sintering time is 5-10 h. Compared with the sintering process of other solid electrolytes, the lithium titanate lanthanum composite material can be synthesized at a relatively low temperature, and the volatilization of a lithium source can be effectively avoided.
The lithium lanthanum titanate with the calcium mineral structure can be synthesized by the prior art, such as a solid phase method, a hydrothermal method or a sol-gel method. The invention provides a solid-phase synthesis method which is characterized by simple synthesis process and low comprehensive cost. The lithium titanate lanthanum is prepared by a method comprising the following steps: ball-milling and mixing the lithium titanate lanthanum synthesis raw material, and sintering to obtain the lithium titanate lanthanum oxide.
2 3 2 3 2The method comprises the steps of preparing lanthanum lithium titanate, preparing lanthanum titanium titanate, preparing lanthanum lithium titanate, preparing lanthanum titanium, pre-sintering at 900 ℃ of 700-900 ℃, heating to 1200 ℃ of 1100-1200 ℃, and then re-sintering, wherein the pre-sintering time is 3-5h, and the re-sintering time is 5-8 h.
Li 3 OX with an anticalcite structure can be prepared by a similar solid-phase synthesis method, specifically, the Li 3 OX is prepared by a method comprising the following steps of ball-milling and mixing Li 3 OX synthetic raw materials, and sintering the mixture to obtain the Li 3 OX synthetic raw materials, wherein the Li 2 O and LiX can be used as the Li 3 OX synthetic raw materials, and the mass ratio of the Li 2 O to the LiX can be controlled to be (1-1.1) to (1-1.1). in the preparation of the Li 3 OX, the Li 3 OX is sintered at 300 ℃ for 5-8 hours to obtain the anticalcite structure.
A lithium ion solid-state battery comprises a positive electrode, a negative electrode and a diaphragm, wherein the positive electrode contains a positive electrode active substance and a lithium lanthanum titanate composite material, the lithium lanthanum titanate composite material is formed by compounding Li 3 OX with an anti-calcium state ore structure and lithium lanthanum titanate with a calcium state ore structure, Li 3 OX is distributed at a crystal boundary between lithium lanthanum titanate crystal grains and partially diffuses into the lithium lanthanum titanate crystal grains, the chemical formula of the lithium lanthanum titanate is Li 3x La 2/3-x TiO 3, X is more than 0 and less than 0.16, and in the Li 3 OX, X is halogen.
In the lithium ion solid-state battery, the diaphragm can adopt the existing solid electrolyte diaphragm, the negative electrode can adopt metal lithium or other conventional negative electrodes, and the solid-state battery containing the lithium titanate lanthanum composite material has excellent cycle stability and reversibility.
An electrolyte layer contains the lithium titanate lanthanum composite material. The electrolyte layer is formed by coating a lithium titanate lanthanum composite material and a binder, wherein the mass ratio of the lithium titanate lanthanum composite material to the binder is (85-95): (5-15). The thickness of the electrolyte layer can be controlled to 15-35 μm.
The active material layer can be controlled to be 10-30 mu m, the active material layer can further contain substances such as a conductive agent, a binder and the like so as to improve the comprehensive performance of the anode, the active material layer is composed of the anode active material, the solid electrolyte, the conductive agent and the binder, the mass ratio of the components is (61-91): (3-13): (3-13): the selection of the anode active material and the conductive agent is not particularly limited, the anode active material can be a conventional anode material such as LiFePO 4, NCM, LiCoO 2 and the conductive agent can be conductive carbon black.
The electrolyte can be the electrolyte of the existing lithium ion battery, preferably, the electrolyte consists of lithium salt and organic solvent, the lithium salt can be selected from at least one of LiClO 4, LiPF 6 and LiAsF 6, the organic solvent can be selected from at least one of Propylene Carbonate (PC), Ethylene Carbonate (EC) and Ethylene Propylene Carbonate (EPC), the concentration of the lithium salt can be selected between 0.5 and 1.5mol/L, and the electrolyte is preferably an anhydrous propylene carbonate solution of LiClO 4 from the aspects of comprehensive performance and cost of the battery, and the concentration of the LiClO 4 is 1 mol/L.
Drawings
Fig. 1 is a schematic structural diagram of a lithium lanthanum titanate composite material of the present invention;
Fig. 2 is a schematic structural view of a lithium ion solid-state battery according to the present invention;
FIG. 3 is the XRD patterns of the raw materials Li 3 OCl and LLTO;
FIG. 4 is an XRD pattern of lanthanum lithium titanate composites of examples 1-6;
FIG. 5 is a graph of impedance of lanthanum lithium titanate composite materials of examples 1-4 and a pure lanthanum lithium titanate material of a comparative example;
FIG. 6 is a graph of impedance of lanthanum lithium titanate composites of examples 5-6;
Fig. 7 is a constant current charge and discharge curve of the solid-state battery of example 2;
Fig. 8 is a graph of the cycling performance and the library efficiency of the solid-state battery of example 2 at different rates;
Fig. 9 is a rate charge and discharge curve of the solid-state battery of example 2.
Detailed Description
In the following examples, Li 0.5 La 0.5 TiO 3 is prepared by wet ball milling 3.879g Li 2 CO 3, 16.2905g La 2 O 3 and 15.974g TiO 2 at 350r/min for 10h, wherein ethanol is used as a dispersant, drying and taking out at 60 ℃, pre-sintering the ball-milled raw material powder at 800 ℃ for 4h, then heating to 1150 ℃ and sintering for 6h, and grinding the sintered product into micro-nano powder for later use.
The Li 0.35 La 0.55 TiO 3 is prepared by the following steps of taking Li 2 CO 3, La 2 O 3 and TiO 2 according to the molar ratio of Li to La to Ti of 0.35:0.55:1 respectively, carrying out wet ball milling for 10 hours at the speed of 350r/min, taking out after drying at the temperature of 60 ℃, presintering the powder for 4 hours at the temperature of 800 ℃, then heating to 1150 ℃ and then sintering for 6 hours, and grinding the sintered product into micro-nano powder for later use.
The Li 3 OCl is prepared by ball milling 3.2868g Li 2 O and 4.339g LiCl at 350r/min for 5h, sintering at 255 deg.C for 6h to obtain Li 3 OCl with anti-perovskite structure, and grinding into micro-nano powder for use, wherein the processes are carried out in oxygen-free environment.
Example 1
The lithium titanate lanthanum composite material is formed by compounding Li 0.5 La 0.5 TiO 3 and Li 3 OCl, a structural schematic diagram is shown in FIG. 1, Li 3 OX is distributed at grain boundaries among lithium titanate lanthanum crystal grains, part of Li 3 OX is further diffused into the lithium titanate lanthanum crystal grains, and the mass ratio of Li 0.5 La 0.5 TiO 3 to Li 3 OCl is 9.99: 0.01.
The preparation method of the lanthanum lithium titanate composite material comprises the following steps of grinding and mixing 9.99g of Li 0.5 La 0.5 TiO 3 and 0.01g of Li 3 OCl, weighing 1g of mixed powder, pressing the mixed powder into a tablet in a mold with the diameter of 16mm, keeping the pressure of the tablet at 20MPa for 2min, and calcining the tablet at 1250 ℃ for 6h in an argon protective atmosphere to obtain the lanthanum lithium titanate composite material.
The lithium ion solid-state battery of this embodiment is shown in fig. 2, and includes a positive electrode, a negative electrode 5, and a separator 4, where the positive electrode includes an aluminum current collector 1, an active material layer 2 disposed on the aluminum current collector, and a solid electrolyte layer 3 coated on a surface of the active material layer, and the solid electrolyte layer contains the lithium titanate lanthanum composite material of this embodiment, and the specific preparation process is as follows:
Mixing a positive electrode active material (LiFePO 4), conductive carbon black, PVDF and the lithium titanate lanthanum composite material in the embodiment according to the mass ratio of 70:10:10:10, adding N-methyl pyrrolidone to prepare positive electrode slurry with proper viscosity, stirring for later use, coating the positive electrode slurry on an aluminum foil on a coating machine, controlling the thickness to be 20 mu m, drying the aluminum foil in a blast drying box at 60 ℃ for 2-6h, transferring the aluminum foil to a vacuum drying box, performing vacuum drying at 100 ℃ to form an active material layer, mixing the lithium titanate lanthanum composite material and the PVDF according to the mass ratio of 90:10, preparing electrolyte slurry by taking N-methyl pyrrolidone as a solvent, scraping the electrolyte slurry on the active material layer, controlling the thickness to be 20 mu m, transferring the mixture to the blast drying box, drying at 70 ℃ for 6h, transferring the dried mixture to the vacuum drying box, and performing vacuum drying at 100 ℃ to obtain the positive electrode.
And (3) a diaphragm, namely dropping electrolyte on two sides of the PP diaphragm until the diaphragm does not absorb the electrolyte any more, or immersing the PP diaphragm in the electrolyte, taking out the PP diaphragm, and standing until no electrolyte naturally drops to realize the infiltration of the electrolyte, wherein the electrolyte is 1mol/L of LiClO 4 anhydrous propylene carbonate solution.
negative electrode: a lithium sheet.
And assembling the positive electrode, the negative electrode and the diaphragm into a solid-state battery.
Example 2
The lithium lanthanum titanate composite material of the embodiment has the substantially same structure as that of the embodiment 1, and is only different from the embodiment 1 in that the mass ratio of Li 0.5 La 0.5 TiO 3 to Li 3 OCl is 9.985: 0.015.
The preparation method of the lithium titanate lanthanum composite material of the embodiment refers to the preparation method of the embodiment 1.
A lithium-ion solid-state battery of this example was prepared with reference to example 1.
Example 3
The lithium lanthanum titanate composite material of the embodiment has the same structure as the embodiment 1, and is only different from the embodiment 1 in that the mass ratio of Li 0.5 La 0.5 TiO 3 to Li 3 OCl is 9.98: 0.02.
The preparation method of the lithium titanate lanthanum composite material of the embodiment is basically the same as that of the embodiment 1, except that the calcination condition is that the calcination is carried out at 1100 ℃ for 7 h.
The lithium ion solid-state battery of the present example is substantially the same as example 1 except that the active material layer of the positive electrode has a thickness of 30 μm, the active material layer is composed of a positive electrode active material, conductive carbon black, PVDF and a lithium titanate lanthanum composite material, and the mass ratio of the components is 91:3:3: 3; the thickness of the solid electrolyte layer on the active material layer is 35 mu m, and the mass ratio of the lithium lanthanum titanate composite material to the PVDF in the solid electrolyte layer is 95: 5.
Example 4
The lithium lanthanum titanate composite material of the embodiment has the same structure as the embodiment 1, and is only different from the embodiment 1 in that the mass ratio of Li 0.5 La 0.5 TiO 3 to Li 3 OCl is 9.97: 0.03.
The preparation method of the lithium titanate lanthanum composite material of the embodiment is basically the same as that of the embodiment 1, except that the calcination condition is that the calcination is carried out at 1000 ℃ for 8 h.
The lithium ion solid-state battery of the present example is substantially the same as example 1 except that the active material layer of the positive electrode has a thickness of 10 μm, the active material layer is composed of a positive electrode active material, conductive carbon black, PVDF and a lithium titanate lanthanum composite material, and the mass ratio of the components is 61:13:13: 13; the thickness of the solid electrolyte layer on the active material layer is 15 mu m, and the mass ratio of the lithium titanate lanthanum composite material to the PVDF in the solid electrolyte layer is 80: 20.
Example 5
the lithium lanthanum titanate composite material of the embodiment has the same structure as the embodiment 1, and is only different from the embodiment 1 in that the mass ratio of Li 0.5 La 0.5 TiO 3 to Li 3 OCl is 9.96: 0.04.
The preparation method of the lithium titanate lanthanum composite material of the embodiment refers to the preparation method of the embodiment 1.
A lithium-ion solid-state battery of this example was prepared with reference to example 1.
Example 6
The lithium lanthanum titanate composite material of the embodiment has the same structure as the embodiment 1, and is only different from the embodiment 1 in that the mass ratio of Li 0.5 La 0.5 TiO 3 to Li 3 OCl is 9.92: 0.08.
The preparation method of the lithium titanate lanthanum composite material of the embodiment refers to the preparation method of the embodiment 1.
a lithium-ion solid-state battery of this example was prepared with reference to example 1.
examples 7 to 12
The lithium lanthanum titanate composite material of the embodiment has the same structure as the embodiment 1, and is different from the lithium lanthanum titanate composite material of the embodiment only in that the lithium lanthanum titanate composite material is formed by Li 0.35 La 0.55 TiO 3 and Li 3 OCl, and the mass ratios of the Li 0.35 La 0.55 TiO 3 to the Li 3 OCl are 9.99: 0.01, 9.985: 0.015, 9.98: 0.02, 9.97: 0.03, 9.96: 0.04 and 9.92: 0.08 respectively.
Lanthanum lithium titanate composites of examples 7-12 can be prepared by reference to the method of example 1, and lithium ion solid state batteries can be prepared according to the method of example 1 on the basis of the corresponding lanthanum lithium titanate composites.
Comparative example
1g of Li 0.5 La 0.5 TiO 3 powder prepared in example 1 was put into a mold with a diameter of 16mm to be pressed into tablets under a pressure of 20MPa for 2min, and then calcined at 1350 ℃ for 6h to obtain a pure LLTO ceramic electrolyte material.
Test example 1
XRD phase analyses were performed on the raw material powder and the product powder, and the results are shown in fig. 3 and 4.
FIG. 3 is an XRD pattern of synthesized Li 3 OCl and LLTO (Li 0.5 La 0.5 TiO 3) of the present invention, and it can be seen that Li 3 OCl and LLTO can be conveniently synthesized by a solid phase method.
Fig. 4 is an XRD pattern of the lanthanum lithium titanate composite materials of examples 1 to 6, and it can be seen that the lanthanum lithium titanate composite materials prepared by the examples have a composite structure of Li 3 OCl and LLTO (Li 0.5 La 0.5 TiO 3).
test example 2
The surfaces of both sides of the lithium titanate lanthanum composite material of examples 1 to 6 in the thickness direction were coated with high purity silver paste or gold plated, and placed in an ac impedance tester to test an ac impedance spectrum, and fitting was performed using an electrochemical equivalent circuit and processing software to obtain values of the grain conductivity, the grain boundary conductivity, and the total conductivity, and the results are shown in fig. 5, fig. 6, and table 1.
TABLE 1 Ionic conductivities (30 ℃ C.) of lanthanum lithium titanate composites of examples 1-6
(σ b, σ sb, σ b+sb are grain conductivity, grain boundary conductivity, and total conductivity, respectively.)
FIG. 5 is a resistance diagram of lanthanum lithium titanate composite materials of examples 1-4, and it can be seen that as the amount of Li 3 OCl introduced into LLTO increases, the grain boundary resistance increases after decreasing, and LLTO +2 wt.% Li 3 OCl has the lowest grain boundary resistance, and the insets are the intragranular resistance, and also decrease at the same time, which means that the grain boundary ionic conductance is increased.
Fig. 6 is a resistance diagram of the lithium lanthanum titanate composite materials of examples 5 to 6, and it can be seen that as the amount of Li 3 OCl introduced into LLTO is further increased to more than 3%, the grain boundary resistance is greatly increased, and the ion conduction capability is reduced.
Test example 3
The test examples were conducted to examine the constant current charge/discharge performance and rate capability of the lithium ion solid-state battery of example 2, and the results are shown in fig. 7 to 9.
Fig. 7 is a constant current charge and discharge curve of the solid-state battery of example 2, and it can be seen that the first charge specific capacity of the battery is about 153mAh/g, the specific capacity after 40 weeks is about 142mAh/g, wherein the charge voltage plateau is about 3.6V and the discharge voltage plateau is about 3.35V.
Fig. 8 shows the cycle performance and the storage efficiency of the solid-state battery of example 2 at 35 ℃ and 0.05C rate, and it can be seen that the battery capacity retention rate was 92% and the storage efficiency was close to 100% in the first 40 weeks.
Fig. 9 is a rate charge and discharge curve of the solid-state battery of example 2, and it can be seen that the battery has a certain cycle stability and good reversibility.
As can be seen from the above electrochemical tests, the solid-state battery prepared in example 2 has excellent cycle stability and reversibility, and meets the application requirements of commercial batteries.
In other embodiments of the lithium lanthanum titanate composite material of the present invention, the structures of Li 3x La 2/3-x TiO 3 are not limited to Li 0.5 La 0.5 TiO 3 and Li 0.35 La 0.55 TiO 3, the structure of Li 3 OX is not limited to Li 3 OCl, and the principles of modifying the grain boundary of Li 3x La 2/3- x TiO 3 by Li 3 OX with other structures, improving the grain boundary conductance and the total conductance are the same, and the grain boundary conductance improving effect equivalent to that of embodiment 2 can be achieved.
in other embodiments of the lithium ion solid-state battery, the solid electrolyte in the active material layer may be other types of solid electrolytes, the addition ratio of the positive electrode active material and the solid electrolyte may be adjusted according to the type of the positive electrode material, the type of the battery, and the type of the solid electrolyte, and the addition ratio of the solid electrolyte, the binder in the electrolyte layer, the thickness of the active material layer, and the thickness of the electrolyte layer may be adjusted within the range defined by the present invention, so that the effect equivalent to that of embodiment 2 can be obtained.
Claims (9)
1. The lithium titanate lanthanum composite material is characterized by being compounded by Li 3 OX with an anti-calcium state ore structure and lithium titanate lanthanum with a calcium state ore structure, wherein Li 3 OX is distributed at grain boundaries among lithium titanate lanthanum grains and diffuses into the lithium titanate lanthanum grains, the chemical formula of the lithium titanate lanthanum is Li 3x La 2/3-x TiO 3, X is more than 0 and less than 0.16, and in Li 3 OX, X is halogen.
2. The lanthanum lithium titanate composite material of claim 1, characterized in that the mass ratio of Li 3 OX to Li 3x La 2/3-x TiO 3 is m (1-m), wherein 0 < m < 0.2.
3. A preparation method of a lithium titanate lanthanum composite material is characterized by comprising the following steps of ball-milling and mixing Li 3 OX with an anti-calcium state ore structure and lithium titanate lanthanum with a calcium state ore structure, pressing and sintering to obtain the lithium titanate lanthanum, wherein the chemical formula of the lithium titanate lanthanum is Li 3x La 2/3-x TiO 3, X is more than 0 and less than 0.16, and in Li 3 OX, X is halogen.
4. The method of preparing a lanthanum lithium titanate composite material of claim 3, wherein the pressure during pressing is 5-30 MPa.
5. The method for preparing the lanthanum lithium titanate composite material of claim 3, wherein the sintering temperature is 400-1250 ℃, and the sintering time is 5-10 h.
6. A lithium ion solid state battery using the lanthanum lithium titanate composite material of claim 1.
7. The lithium ion solid state battery of claim 6, wherein the positive electrode of the battery comprises a current collector, an active material layer coated on the current collector, and an electrolyte layer coated on the active material layer, wherein the electrolyte layer is composed of a lanthanum lithium titanate composite and a binder, and the mass ratio of the lanthanum lithium titanate composite to the binder is (85-95): (5-15).
8. The lithium ion solid-state battery according to claim 7, wherein the active material layer is composed of a positive electrode active material, a solid electrolyte, a conductive agent and a binder, and the mass ratio of each component is (61-91): (3-13): (3-13): (3-13).
9. The lithium ion solid state battery according to any one of claims 6 to 8, wherein a separator for the battery is adsorbed with an electrolyte.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111463477A (en) * | 2020-03-13 | 2020-07-28 | 深圳大学 | Composite solid electrolyte with enhanced stability of fluorinated additive and preparation method thereof |
| CN111463479A (en) * | 2020-04-10 | 2020-07-28 | 上海电气集团股份有限公司 | Solid electrolyte, composite solid electrolyte, lithium ion battery and preparation method and application thereof |
| CN111725561A (en) * | 2020-07-31 | 2020-09-29 | 南方科技大学 | Solid electrolyte, preparation method thereof and all-solid-state battery |
| CN113372110A (en) * | 2021-05-28 | 2021-09-10 | 北京高压科学研究中心 | Method for preparing perovskite type solid electrolyte lanthanum lithium titanate based on high-temperature and high-pressure synthesis |
| CN113620708A (en) * | 2020-05-08 | 2021-11-09 | 康宁股份有限公司 | Garnet-lithium titanate composite electrolyte |
| CN114230343A (en) * | 2021-12-27 | 2022-03-25 | 安徽壹石通材料科技股份有限公司 | Solid electrolyte with low sintering temperature and solid lithium battery |
| WO2023189375A1 (en) * | 2022-03-31 | 2023-10-05 | 株式会社村田製作所 | Solid-state electrolyte for solid-state battery, solid-state battery, and battery package |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101325094A (en) * | 2008-07-25 | 2008-12-17 | 清华大学 | Lithium lanthanum titanium oxygen LLTO composite solid-state electrolyte material and synthesizing method thereof |
| WO2014150763A1 (en) * | 2013-03-15 | 2014-09-25 | Los Alamos National Security, Llc | Anti-perovskite solid electrolyte compositions |
| CN104466239A (en) * | 2014-11-27 | 2015-03-25 | 中国科学院物理研究所 | Lithium-enriched anti-perovskite sulfides, solid electrolyte material containing lithium-enriched anti-perovskite sulfides and application of solid electrolyte material |
| CN106602138A (en) * | 2017-01-17 | 2017-04-26 | 哈尔滨工业大学无锡新材料研究院 | Solid polymer electrolyte added with high-concentration lithium salt and preparation method thereof |
| CN107195859A (en) * | 2017-05-19 | 2017-09-22 | 中国电子科技集团公司第十八研究所 | Preparation method of dispersion battery |
| CN107403955A (en) * | 2017-08-04 | 2017-11-28 | 郑州新世纪材料基因组工程研究院有限公司 | A kind of dimorphism anti-perovskite lithium ion solid electrolyte and preparation method thereof, application |
-
2018
- 2018-05-30 CN CN201810541279.2A patent/CN110556571B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101325094A (en) * | 2008-07-25 | 2008-12-17 | 清华大学 | Lithium lanthanum titanium oxygen LLTO composite solid-state electrolyte material and synthesizing method thereof |
| WO2014150763A1 (en) * | 2013-03-15 | 2014-09-25 | Los Alamos National Security, Llc | Anti-perovskite solid electrolyte compositions |
| CN104466239A (en) * | 2014-11-27 | 2015-03-25 | 中国科学院物理研究所 | Lithium-enriched anti-perovskite sulfides, solid electrolyte material containing lithium-enriched anti-perovskite sulfides and application of solid electrolyte material |
| CN106602138A (en) * | 2017-01-17 | 2017-04-26 | 哈尔滨工业大学无锡新材料研究院 | Solid polymer electrolyte added with high-concentration lithium salt and preparation method thereof |
| CN107195859A (en) * | 2017-05-19 | 2017-09-22 | 中国电子科技集团公司第十八研究所 | Preparation method of dispersion battery |
| CN107403955A (en) * | 2017-08-04 | 2017-11-28 | 郑州新世纪材料基因组工程研究院有限公司 | A kind of dimorphism anti-perovskite lithium ion solid electrolyte and preparation method thereof, application |
Non-Patent Citations (1)
| Title |
|---|
| YIJUN TIAN ET AL: "Li6.75La3Zr1.75Ta0.25O12@amorphous Li3OCl composite electrolyte for solid state lithium-metal batteries", 《ENERGY STORAGE MATERIALS》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111463477A (en) * | 2020-03-13 | 2020-07-28 | 深圳大学 | Composite solid electrolyte with enhanced stability of fluorinated additive and preparation method thereof |
| CN111463477B (en) * | 2020-03-13 | 2021-08-03 | 深圳大学 | Composite solid electrolyte with enhanced stability of fluorinated additive and preparation method thereof |
| CN111463479A (en) * | 2020-04-10 | 2020-07-28 | 上海电气集团股份有限公司 | Solid electrolyte, composite solid electrolyte, lithium ion battery and preparation method and application thereof |
| CN111463479B (en) * | 2020-04-10 | 2022-11-22 | 上海电气集团股份有限公司 | Solid electrolyte, composite solid electrolyte, lithium ion battery, and preparation method and application thereof |
| CN113620708A (en) * | 2020-05-08 | 2021-11-09 | 康宁股份有限公司 | Garnet-lithium titanate composite electrolyte |
| CN113620708B (en) * | 2020-05-08 | 2024-03-22 | 康宁股份有限公司 | Garnet-lithium titanate composite electrolyte |
| CN111725561A (en) * | 2020-07-31 | 2020-09-29 | 南方科技大学 | Solid electrolyte, preparation method thereof and all-solid-state battery |
| CN111725561B (en) * | 2020-07-31 | 2021-09-28 | 南方科技大学 | Solid electrolyte, preparation method thereof and all-solid-state battery |
| CN113372110A (en) * | 2021-05-28 | 2021-09-10 | 北京高压科学研究中心 | Method for preparing perovskite type solid electrolyte lanthanum lithium titanate based on high-temperature and high-pressure synthesis |
| CN114230343A (en) * | 2021-12-27 | 2022-03-25 | 安徽壹石通材料科技股份有限公司 | Solid electrolyte with low sintering temperature and solid lithium battery |
| WO2023189375A1 (en) * | 2022-03-31 | 2023-10-05 | 株式会社村田製作所 | Solid-state electrolyte for solid-state battery, solid-state battery, and battery package |
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