CN117080541A - Solid electrolyte, preparation method thereof, solid lithium ion battery and electric equipment - Google Patents
Solid electrolyte, preparation method thereof, solid lithium ion battery and electric equipment Download PDFInfo
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- CN117080541A CN117080541A CN202311142574.8A CN202311142574A CN117080541A CN 117080541 A CN117080541 A CN 117080541A CN 202311142574 A CN202311142574 A CN 202311142574A CN 117080541 A CN117080541 A CN 117080541A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 52
- 239000007787 solid Substances 0.000 title claims abstract description 44
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000003792 electrolyte Substances 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000000354 decomposition reaction Methods 0.000 claims description 15
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 238000004806 packaging method and process Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000007774 positive electrode material Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000005457 ice water Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002955 isolation Methods 0.000 description 6
- 241000773945 Trimusculidae Species 0.000 description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910011322 LiNi0.6Mn0.2Co0.2O2 Inorganic materials 0.000 description 1
- 229910015965 LiNi0.8Mn0.1Co0.1O2 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 excess ammonia gas Chemical compound 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Classifications
-
- 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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- Secondary Cells (AREA)
- Conductive Materials (AREA)
Abstract
The invention relates to the technical field of solid-state batteries, in particular to a solid-state electrolyte, a preparation method thereof, a solid-state lithium ion battery and electric equipment. The chemical formula of the solid electrolyte is LiBH 4 (NH 3 ) x Wherein 0 is<x is less than or equal to 1. The solid electrolyte has high ionic conductivity at 37-50 ℃, and can improve the electrochemical performance of the lithium ion solid battery when used for the lithium ion solid battery.
Description
Technical Field
The invention relates to the technical field of solid-state batteries, in particular to a solid-state electrolyte, a preparation method thereof, a solid-state lithium ion battery and electric equipment.
Background
Lithium ion batteries have received attention as a new energy storage device in recent years. The lithium ion battery has been widely used in the fields of electronic devices, electric vehicles, and the like because of its advantages such as high energy density, long cycle life, and environmental friendliness. With the maturity of technology, the energy density of 300Wh/kg is obtained in the existing lithium ion battery, however, the energy density, safety and stability of the battery are more severely required by the modern society. The development of advanced all-solid-state lithium ion batteries by replacing organic electrolyte with solid-state electrolyte is considered as a necessary way to improve battery energy density and solve battery safety.
LiBH 4 The base solid-state electrolyte has attracted attention in recent years due to its advantages of light weight, low grain boundary resistance, good ion selectivity, good stability to Li, excellent mechanical properties, and the like. Although LiBH 4 At high temperature%>110 ℃ exhibits a temperature of more than 10 DEG C -3 S cm -1 But its low ionic conductivity at temperatures below 40 c greatly limits its practical use in all-solid-state batteries.
In view of this, the present invention has been made.
Disclosure of Invention
A first object of the present invention is to provide a solid electrolyte having high ionic conductivity at 37 to 50 ℃.
A second object of the present invention is to provide a method for producing a solid electrolyte.
A third object of the present invention is to provide a solid-state lithium ion battery.
A fourth object of the present invention is to provide a powered device.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
the invention provides a solid electrolyte, which has a chemical formula of LiBH 4 (NH 3 ) x Wherein 0 is<x≤1。
The invention also provides a preparation method of the solid electrolyte, which comprises the following steps:
LiBH 4 (NH 3 ) 2 and (3) carrying out decomposition reaction under vacuum condition to obtain the solid electrolyte.
The invention also provides a solid-state lithium ion battery, which comprises the solid-state electrolyte.
The invention further provides electric equipment, which comprises the solid-state lithium ion battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) The solid electrolyte provided by the invention has high ion conductivity at 37-50 ℃, and can be used for a lithium ion solid battery to improve the electrochemical performance of the lithium ion solid battery, in particular to improve the cycle performance.
(2) The preparation method of the solid electrolyte provided by the invention is based on LiBH 4 (NH 3 ) 2 LiBH 4 (NH 3 ) x (0<The solid electrolyte for the lithium ion solid-state battery is prepared by the liquid-solid conversion reaction between x is less than or equal to 1), the solid-solid interface problem between the positive electrode material and the solid electrolyte and the solid-solid interface problem between the solid electrolyte and lithium metal can be effectively solved, high lithium ion conductivity can be realized, and LiBH is adopted 4 (NH 3 ) x (0<x.ltoreq.1) the solid-state battery of the solid-state electrolyte has excellent cycle performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a LiBH according to the present invention 4 NH 3 LiBH 4 (NH 3 ) 2 Is a physical diagram of (a); wherein FIG. 1 (a) is LiBH 4 NH 3 FIG. 1 (b) is a physical diagram of LiBH 4 (NH 3 ) 2 Is a physical diagram of (a);
fig. 2 is an electrochemical performance test chart of the solid-state lithium ion battery prepared in example 1 according to the present invention.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and detailed description, but it will be understood by those skilled in the art that the examples described below are some, but not all, examples of the present invention, and are intended to be illustrative of the present invention only and should not be construed as limiting the scope of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In a first aspect, the present invention provides a high ionic conductivity solid state electrolyte for a lithium ion solid state battery, the solid state electrolyte having the formula LiBH 4 (NH 3 ) x Wherein 0 is<x≤1。
LiBH as described above 4 (NH 3 ) x Including but not limited to a point value of any one of 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0 or a range value therebetween.
The solid electrolyte has high ionic conductivity at 37-50 ℃, and can improve the electrochemical performance of the lithium ion solid battery, especially the cycle performance when being used for the lithium ion solid battery.
In a second aspect, the present invention provides a method for preparing the solid electrolyte, comprising the steps of:
LiBH is carried out 4 (NH 3 ) 2 Placing the solid electrolyte in a vacuum condition for decomposition reaction, and obtaining the solid electrolyte LiBH after the decomposition reaction is completed 4 (NH 3 ) x (0<x≤1)。
Wherein LiBH 4 (NH 3 ) 2 In liquid state, liBH 4 (NH 3 ) x (0<x is less than or equal to 1) is solid.
The invention is based on LiBH 4 (NH 3 ) 2 LiBH 4 (NH 3 ) x (0<The solid electrolyte for the lithium ion solid-state battery is prepared by the liquid-solid conversion reaction between x is less than or equal to 1), so that the solid-solid interface problem between the positive electrode material and the solid electrolyte and the solid-solid interface problem between the solid electrolyte and lithium metal can be effectively solved, and high lithium ion conductivity can be realized, and therefore, liBH is adopted 4 (NH 3 ) x (0<x.ltoreq.1) solid-state batteries of solid-state electrolytes have long cycle performance.
The principle of the above decomposition reaction is as follows: liBH 4 (NH 3 ) 2 ＝LiBH 4 (NH 3 ) x +(2-x)NH 3 。
FIG. 1 is LiBH 4 NH 3 (i.e., x=1) and LiBH 4 (NH 3 ) 2 Is a real image of (a). Referring to FIG. 1 (a), liBH according to the present invention 4 NH 3 It can be seen that it is solid. Referring to FIG. 1 (b), there is shown LiBH according to the present invention 4 (NH 3 ) 2 Is in a liquid state.
In the invention, the solid electrolyte LiBH can be accurately regulated and controlled by controlling the vacuum degree, the decomposition reaction temperature and the decomposition reaction time 4 (NH 3 ) x X value of (a). Whereas the x value can be determined by weighing (i.e. testing the mass).
In some embodiments, when 0< x.ltoreq.1, the greater the value of x, the higher the ionic conductivity of the solid state electrolyte.
In some specific embodiments, the vacuum condition has a vacuum level of 10 or less -5 pa, including but not limited to 1X 10 - 5 pa、9×10 -6 pa、8×10 -6 pa、7×10 -6 pa、6×10 -6 pa、5×10 -6 pa、3×10 -6 pa、1×10 -6 A point value of any one of pa or a range value between any two.
The vacuum degree can ensure that the decomposition reaction is smoothly carried out, ensure a faster reaction rate and shorten the reaction time.
In some specific embodiments, the decomposition reaction temperature is 10-60 ℃, including but not limited to 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃ or any range between any two of the point values.
The adoption of the reaction temperature is favorable for smooth proceeding of the decomposition reaction, and the rapid extraction of ammonia gas is avoided.
In some embodiments, the time of the decomposition reaction is 0.2 to 6 hours, including but not limited to a point value of any one of 0.2 hours, 0.3 hours, 0.5 hours, 1 hour, 1.5 hours, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, or a range value between any two.
In some embodiments, the LiBH 4 (NH 3 ) 2 The preparation method of the composition specifically comprises the following steps: under vacuum, liBH 4 With ammonia (NH) 3 ) Mixing and carrying out a synthesis reaction to obtain the LiBH 4 (NH 3 ) 2 。
In some specific embodiments, the temperature of the chemical combination reaction is from-5 ℃ to 5 ℃, including, but not limited to, any one point value or a range value between any two of-5 ℃, -4 ℃, -3 ℃, -2 ℃, -1 ℃,0 ℃,1 ℃, 2 ℃, 3 ℃, 4 ℃, 5 ℃.
In some embodiments, the combining reaction is performed in an ice-water bath.
In some specific embodiments, the time of the chemical combination reaction is 0.5 to 6 hours, including but not limited to a point value of any one of 0.5 hours, 1 hour, 1.5 hours, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, or a range value between any two.
In some embodiments, liBH 4 With NH 3 The molar ratio of (2) is 1: 2-5, including but not limited to any one of the dot values or range values between any two of 1:2, 1:2.1, 1:2.2, 1:2.3, 1:2.5, 1:2.8, 1:3, 1:3.5, 1:4, 1:4.5, 1:5.
In some specific embodiments, ammonia gas, i.e., excess ammonia gas, is continuously introduced into the reaction vessel after the evacuation until all of the solid state is converted to liquid and the reaction is completed.
In a third aspect, the present invention provides a solid state lithium ion battery comprising said solid state electrolyte.
LiBH using the above solid electrolyte 4 (NH 3 ) x (0<The solid-state lithium ion battery with x less than or equal to 1) has excellent electrochemical performance.
In some specific embodiments, the method for preparing the solid-state lithium ion battery comprises the following steps: installing a diaphragm between the positive pole piece and the negative pole piece, and injecting LiBH (LiBH) into the surface of the diaphragm 4 (NH 3 ) 2 Then carrying out decomposition reaction under vacuum condition to form solid electrolyte LiBH 4 (NH 3 ) x Wherein 0 is<And x is less than or equal to 1, and the solid lithium ion battery is obtained after packaging. The interface problem of solid state battery materials can be solved by completing the liquid-solid conversion in the battery.
Aiming at the problem of solid-state battery material interface, the invention provides a feasible method for preparing a solid-state battery by using LiBH 4 (NH 3 ) 2 LiBH 4 (NH 3 ) x (0<The liquid-solid conversion between x and 1) is directly applied to the solid-state battery, the process is simple and convenient, the batch application is easy, and the long cycle performance of the solid-state battery at 37-50 ℃ can be realized.
In some embodiments, the solid state lithium ion battery comprises at least one of a coin cell battery, a pouch cell battery, and a cylindrical cell battery.
Namely, the solid electrolyte LiBH provided by the invention 4 (NH 3 ) x (0<x.ltoreq.1) can be applied not only in button cells but also in pouch cells and cylindrical cells.
In some embodiments, the positive electrode active material used for the positive electrode sheet in the solid lithium ion battery may be any commercially available positive electrode active material, such as lithium cobaltate, lithium iron phosphate, ternary NCM, NCA, etc., but is not limited thereto.
In some embodiments, the negative electrode material used for the negative electrode sheet in the solid-state lithium ion battery may be any commercially available negative electrode material, such as lithium metal, graphite, hard carbon, and silicon carbon materials, but is not limited thereto.
In some embodiments, the separator in the solid state lithium ion battery includes any commercially available separator, such as, but not limited to, a fiberglass separator.
In a fourth aspect, the invention provides an electric device, comprising the solid-state lithium ion battery.
It is understood that the electric equipment includes any kind of equipment using the solid-state lithium ion battery, such as electric vehicles, electric tools, energy storage systems, intelligent home and internet of things equipment, but is not limited thereto.
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
In the following embodiments of the present invention, the preparation method of the positive electrode sheet includes the following steps: the NMP dispersion of the positive electrode active material (one of lithium cobaltate, lithium iron phosphate and ternary NCM), conductive carbon black, and binder PVDF was slurried with stirring according to the mass ratio of positive electrode active material, conductive carbon black and binder = 96:2:2. And uniformly coating the obtained positive electrode slurry on the surface of a positive electrode current collector aluminum foil with the thickness of 9 mu m, and drying at 120 ℃ to obtain a positive electrode plate with a positive electrode active material layer with the thickness of 100 mu m and single-sided coating of the positive electrode active material.
In the following embodiments of the present invention, the negative electrode is made of one of lithium metal, graphite and silicon-carbon material, and the preparation method of the negative electrode sheet is basically the same as that of the positive electrode sheet, except that the negative electrode sheet is coated on the surface of the copper foil.
In the following examples of the present invention, glass fibers having a thickness of 15 μm were used as the separator.
In the following examples of the invention, liBH was determined by weighing 4 (NH 3 ) x X value of (a).
Example 1
LiBH provided in this embodiment 4 (NH 3 ) 2 The preparation method of the (C) comprises the following steps: liBH is carried out 4 The powder is placed in a round bottom flask and vacuumized to 10 -5 Under Pa, exhausting air in the flask, continuously introducing ammonia gas into the flask, and reacting in an ice-water bath for 2h to obtain liquid LiBH 4 (NH 3 ) 2 。
The solid electrolyte LiBH provided in this example 4 (NH 3 ) x The preparation method of (x=1) and the preparation method of the solid-state lithium ion battery comprise the following steps: liCoO is added with 2 The positive pole piece, the isolating film and lithium metal are sequentially assembled in a CR2032 button shell in a glove box, so that the isolating film is positioned between the positive pole piece and the negative pole piece to play a role in isolation, and 20 mu L of LiBH is injected into the surface of the isolating film 4 (NH 3 ) 2 And vacuuming to 10 at 20deg.C -5 pa or less, and after 4 hours of reaction, liBH 4 (NH 3 ) 2 All are converted into LiBH 4 (NH 3 ) x (x=1), encapsulation.
Example 2
LiBH provided in this embodiment 4 (NH 3 ) 2 The preparation method of the (C) comprises the following steps: liBH is carried out 4 The powder is placed in a round bottom flask and vacuumized to 10 -5 Under Pa, exhausting air in the flask, continuously introducing ammonia gas into the flask, and reacting in an ice-water bath for 3h to obtain liquid LiBH 4 (NH 3 ) 2 。
The solid electrolyte LiBH provided in this example 4 (NH 3 ) x (x=0.75), the preparation method of the solid-state lithium ion battery includes the following steps: liFePO is prepared 4 The positive pole piece, the isolating film and lithium metal are sequentially assembled in a CR2032 button shell in a glove box, so that the isolating film is positioned between the positive pole piece and the negative pole piece to play a role in isolation, and 25 mu L of LiBH is injected into the surface of the isolating film 4 (NH 3 ) 2 And vacuumized at 25 ℃ to 10 -5 pa or less, and after 6 hours of reaction, liBH 4 (NH 3 ) 2 All are converted into LiBH 4 (NH 3 ) x (x=0.75), packaging.
Example 3
LiBH provided in this embodiment 4 (NH 3 ) 2 The preparation method of the (C) comprises the following steps: liBH is carried out 4 The powder is placed in a round bottom flask and vacuumized to 10 -5 Under Pa, exhausting air in the flask, continuously introducing ammonia gas into the flask, and reacting in an ice-water bath for 4h to obtain liquid LiBH 4 (NH 3 ) 2 。
The solid electrolyte LiBH provided in this example 4 (NH 3 ) x The preparation method of (x=0.75) and the preparation method of the solid-state lithium ion battery comprise the following steps: liFePO is prepared 4 The positive pole piece, the isolating film and lithium metal are sequentially assembled in a CR2032 button shell in a glove box, so that the isolating film is positioned between the positive pole piece and the negative pole piece to play a role in isolation, and 25 mu L of LiBH is injected into the surface of the isolating film 4 (NH 3 ) 2 And vacuuming at 40deg.C to 10 -5 pa or less, and after 2 hours of reaction, liBH 4 (NH 3 ) 2 All are converted into LiBH 4 (NH 3 ) x (x=0.75), packaging.
Example 4
LiBH provided in this embodiment 4 (NH 3 ) 2 The preparation method of the (C) comprises the following steps: liBH is carried out 4 The powder is placed in a round bottom flask and vacuumized to 10 -5 Under Pa, exhausting air in the flask, continuously introducing ammonia gas into the flask, and reacting in an ice-water bath for 5h to obtain liquid LiBH 4 (NH 3 ) 2 。
The solid electrolyte LiBH provided in this example 4 (NH 3 ) x The preparation method of (x=0.5) and the preparation method of the solid-state lithium ion battery comprise the following steps: NCM622 (LiNi 0.6 Mn 0.2 Co 0.2 O 2 ) The positive pole piece, the isolating film and lithium metal are sequentially assembled in a CR2032 button shell in a glove box, so that the isolating film is positioned between the positive pole piece and the negative pole piece to play a role in isolation, and 25 mu L of LiBH is injected into the surface of the isolating film 4 (NH 3 ) 2 And vacuuming at 60deg.C to 10 -5 pa, reacting for 15min, liBH 4 (NH 3 ) 2 All are converted into LiBH 4 (NH 3 ) x (x=0.5), packaging.
Example 5
LiBH provided in this embodiment 4 (NH 3 ) 2 The preparation method of the (C) comprises the following steps: liBH is carried out 4 The powder is placed in a round bottom flask and vacuumized to 10 -5 Under Pa, exhausting air in the flask, continuously introducing ammonia gas into the flask, and reacting in an ice-water bath for 6h to obtain liquid LiBH 4 (NH 3 ) 2 。
The solid electrolyte LiBH provided in this example 4 (NH 3 ) x The preparation method of (x=0.5) and the preparation method of the solid-state lithium ion battery comprise the following steps: liFePO is prepared 4 The positive pole piece, the isolating film and the graphite negative pole piece are sequentially stacked, so that the isolating film is positioned between the positive pole piece and the negative pole piece to play a role in isolation, and then the electrode assembly is obtained by winding. After welding the electrode lug, the electrode assembly is put into an aluminum plastic film packaging shell, and is placed into a vacuum oven at 80 ℃ to be dried for 12 hours to remove water, and then 25 mu LLiBH is injected 4 (NH 3 ) 2 And vacuumized at 25 ℃ to 10 -5 pa or less, and after 4 hours of reaction, liBH 4 (NH 3 ) 2 All are converted into LiBH 4 (NH 3 ) x (x=0.5), packaging.
Example 6
LiBH provided in this embodiment 4 (NH 3 ) 2 The preparation method of the (C) comprises the following steps of: liBH is carried out 4 The powder is placed in a round bottom flask and vacuumized to 10 -5 Under Pa, exhausting air in the flask, continuously introducing ammonia gas into the flask, and reacting in an ice-water bath for 1h to obtain liquid LiBH 4 (NH 3 ) 2 。
The solid electrolyte LiBH provided in this example 4 (NH 3 ) x The preparation method of (x=0.75) and the preparation method of the solid-state lithium ion battery comprise the following steps: NCM811 (LiNi 0.8 Mn 0.1 Co 0.1 O 2 ) The positive pole piece, the isolating membrane and the silicon-carbon negative pole piece (Bei Terui, DXA5 silicon-carbon negative pole) are stacked in sequence, so that the isolating membrane is positioned between the positive pole piece and the negative pole piece to play a role of isolation, and then the electrode assembly is obtained by winding. After welding the electrode lugs, the electrode assembly is put into an aluminum plastic film packaging shell, and is placed in a vacuum oven at 80 ℃ to be dried for 12 hours to remove water, and then 20 mu L LiBH is injected 4 (NH 3 ) 2 And vacuumized at 25 ℃ to 10 -5 pa or less, and after 2 hours of reaction, liBH 4 (NH 3 ) 2 All are converted into LiBH 4 (NH 3 ) x (x=0.75), packaging.
Comparative example 1
The solid-state lithium ion battery provided in this comparative example was substantially the same as in example 1, except that LiBH was not injected 4 (NH 3 ) 2 But adds LiBH 4 Solid powder.
Comparative example 2
The solid-state lithium ion battery provided in this comparative example was substantially the same as in example 1, except that LiBH was not injected 4 (NH 3 ) 2 But adds LiBH 4 (NH 3 ) 3 Solid powder.
Experimental example
The solid lithium ion batteries prepared in the above examples and comparative examples were respectively subjected to electrochemical performance test at 40 ℃ and 0.1C, and the results are shown in table 1.
Table 1 electrochemical performance test results for each solid state lithium ion battery
As can be seen from table 1, the solid lithium ion batteries prepared in each example were excellent in electrochemical performance. Whereas comparative examples 1 and 2 were substantially free of charge and discharge.
The solid-state lithium ion battery prepared in example 1 was rated at 100mA g -1 Results of electrochemical performance testing at current density referring to fig. 2, it can be seen that the capacity of the cell remained at 154.6mAh/g after 100 cycles.
Therefore, the solid electrolyte provided by the invention has high ion conductivity, and can be used for the lithium ion solid battery to improve the electrochemical performance of the lithium ion solid battery.
While the invention has been illustrated and described with reference to specific embodiments, it is to be understood that the above embodiments are merely illustrative of the technical aspects of the invention and not restrictive thereof; those of ordinary skill in the art will appreciate that: modifications may be made to the technical solutions described in the foregoing embodiments, or equivalents may be substituted for some or all of the technical features thereof, without departing from the spirit and scope of the present invention; such modifications and substitutions do not depart from the spirit of the corresponding technical solutions; it is therefore intended to cover in the appended claims all such alternatives and modifications as fall within the scope of the invention.
Claims (10)
1. A solid electrolyte is characterized in that the chemical formula of the solid electrolyte is LiBH 4 (NH 3 ) x Wherein 0 is<x≤1。
2. The method for producing a solid electrolyte according to claim 1, comprising the steps of:
LiBH 4 (NH 3 ) 2 and (3) carrying out decomposition reaction under vacuum condition to obtain the solid electrolyte.
3. The solid state electrolysis of claim 2The preparation method of the material is characterized in that the vacuum degree of the vacuum condition is less than or equal to 10 -5 pa。
4. The method for producing a solid electrolyte according to claim 2, wherein the decomposition reaction temperature is 10 to 60 ℃.
5. The method for producing a solid electrolyte according to claim 2, wherein the time for the decomposition reaction is 0.2 to 6 hours.
6. The method for producing a solid electrolyte according to claim 2, wherein the LiBH 4 (NH 3 ) 2 The preparation method of the composition specifically comprises the following steps: under vacuum, liBH 4 Mixing with ammonia gas and carrying out a reaction to obtain the LiBH 4 (NH 3 ) 2 。
7. The method for producing a solid electrolyte according to claim 6, wherein the temperature of the combination reaction is-5 ℃ to 5 ℃;
and/or the time of the combination reaction is 0.5-6 h.
8. A solid state lithium ion battery comprising the solid state electrolyte of claim 1.
9. The solid state lithium ion battery of claim 8, wherein the method of making the solid state lithium ion battery comprises the steps of: installing a diaphragm between the positive pole piece and the negative pole piece, and injecting LiBH (LiBH) into the surface of the diaphragm 4 (NH 3 ) 2 Then carrying out decomposition reaction under vacuum condition to form solid electrolyte LiBH 4 (NH 3 ) x Wherein 0 is<And x is less than or equal to 1, and the solid lithium ion battery is obtained after packaging.
10. A powered device comprising a solid state lithium ion battery as claimed in claim 8 or 9.
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