CN115732751A - Halide solid electrolyte material, preparation method thereof and lithium ion battery - Google Patents
Halide solid electrolyte material, preparation method thereof and lithium ion battery Download PDFInfo
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Abstract
The invention provides a halide solid electrolyte material, a preparation method thereof and a lithium ion battery. The chemical formula of the halide solid electrolyte material is Li a M b Y’ 1‑b X c Cl a+4‑b‑c Wherein M is non-lithium metal ion, M is selected from one or more of the group consisting of Fe, al, ga, ho, yb, Y, sc, in and La series metal elements, Y' is selected from one or more of IVB group elements, X is selected from one or more of the group consisting of F, br and I element, a is 0.5-3,b and is 0.01-0.9, and c is 0.02-5.9. In contrast to conventional halide electrolytes, li a M b Y ’ 1‑b X c Cl a+4‑b‑c Y in (1) ’ The components partially replace the original non-lithium metal components and are compounded with specific types of halogens, so that the ionic conductivity of the halide solid electrolyte material can be effectively improved.
Description
Technical Field
The invention relates to the technical field of lithium ion battery preparation, in particular to a halide solid electrolyte material, a preparation method thereof and a lithium ion battery.
Background
Lithium Ion Batteries (LIBs) have been rapidly developed over the past decade, however, current lithium ion batteries achieve high energy density by increasing battery voltage using organic liquid electrolytes and special additives, which may pose serious safety problems. With the development of new energy power battery technology, the traditional liquid battery can not meet the use requirements of consumers more and more, and the lithium battery technology is developed towards the trend of high safety and high energy density requirements. The development of large-scale energy storage systems such as electric vehicles and power grids is accelerated by the provision of high-energy-density all-solid-state lithium ion batteries, and therefore, the development of high-energy-density and high-safety all-solid-state lithium ion batteries (ASSLBs) becomes a future development trend of the industry.
The key technology of the all-solid-state lithium ion battery as a novel battery energy storage technology is that solid electrolytes (SSEs) eliminate flammable liquid organic electrolytes in the original lithium ion battery, and the safety and the volume energy density are improved through more effective packaging. Although it is now known that fast ion-conducting solids such as sulfides, oxides and phosphates are applied to solid-state batteries, the batteries exhibit disadvantages such as poor mechanical properties and difficulty in processing.
The synthesis method of the halide solid electrolyte material reported at present mainly comprises high-energy ball milling, high-temperature annealing, high-temperature sintering and the traditional liquid phase synthesis process, but the synthesis process has the following defects: (1) In order to avoid the exposure of the electrolyte to the air environment, some previous researches generally adopt a high-energy ball milling and high-temperature annealing mode to synthesize a halide solid electrolyte material, but the energy consumption in the high-temperature synthesis process is high, slurry agglomeration is easily caused during low-speed ball milling, the slurry ball milling is not uniform, the performance of a fired electrolyte battery is poor, the requirement on the type selection of raw materials is high, and the synthesis cost is high; moreover, because the ball milling process has a long period and a complicated process, the method is not suitable for preparing the electrolyte material in batches; (2) The electrolyte material obtained by high-temperature ball milling and high-temperature sintering is easy to agglomerate, so that the ion transmission of the interface between the prepared electrolyte membrane and the positive/negative pole piece is limited, and the performance of the battery is poor; (3) In the traditional liquid phase synthesis process, synthesis reaction and drying treatment are usually carried out in air, more uncontrollable impurity factors can influence the preparation of a precursor due to the fact that the precursor is exposed in the air, and other interference impurities are easily generated in the drying treatment process, so that the conductivity of the prepared product is low.
Therefore, research and development of a preparation method of the halide solid state electrolyte material are important for reducing impurities in the halide solid state electrolyte material and improving the ionic conductivity and stability of the halide solid state electrolyte material, which are important for improving the electrochemical performance of the lithium ion battery.
Disclosure of Invention
The invention mainly aims to provide a halide solid electrolyte material, a preparation method thereof and a lithium ion battery, and aims to solve the problems of poor crystallinity, low ionic conductivity and poor stability of the existing halide solid electrolyte material.
In order to achieve the above object, an aspect of the present invention provides a halide solid state electrolyte material having a chemical formula of Li a M b Y ’ 1-b X c Cl a+4-b-c Wherein M is a non-lithium metal ion, M is one or more selected from the group consisting of Fe, al, ga, ho, yb, Y, sc, in and La series metal elements, and Y is ’ One or more elements selected from group IVB, X is one or more elements selected from the group consisting of F, br and I, and a is 0.5-3,b is 0.01-0.9, and c is 0.02-5.9.
Further, in the halide solid state electrolyte material, Y' is one or more selected from the group consisting of Hf, zr, and Ti.
Further, when M is selected from Yb, or Ho, or a combination of Ho and Fe, Y' is selected from Hf, or Zr, or a combination of Hf and Ti, and X is selected from Br, or I, or a combination of Br and I; preferably, M is Yb, Y' is Hf, and X is Br; more preferably, M is Yb, Y' is Hf, X is Br and a is from 1.1 to 2.8, b is from 0.1 to 0.88 and c is from 0.5 to 2.5; more preferably, a is 1.8 to 2.4, b is 0.1 to 0.8, and c is 0.8 to 2.5.
Further, the halide solid state electrolyte material is selected from Li 2.4 Yb 0.5 Hf 0.5 Br 2 Cl 3.9 、Li 2.1 Yb 0.4 Hf 0.6 Br 1.8 Cl 3.9 、Li 1.8 Yb 0.3 Hf 0.7 Br 1.5 Cl 4 、Li 2.1 Yb 0.5 Hf 0.5 Br 0.8 Cl 4.8 、Li 2.1 Yb 0.1 Hf 0.9 Br 2.5 Cl 3.5 、Li 2.4 Yb 0.6 Hf 0.4 Br 2.2 Cl 3.6 、Li 2.4 Yb 0.8 Hf 0.2 Br 1.6 Cl 4 、Li 2.8 Yb 0.88 Hf 0.12 Br 1.2 Cl 4.72 、Li 2.0 Yb 0.1 Hf 0.9 Br 0.8 Cl 5.1 Or Li 1.1 Yb 0.6 Hf 0.4 Br 0.5 Cl 4 。
Further, the halide solid electrolyte material is a glass phase, a ceramic glass phase or a crystalline phase; preferably, the ionic conductivity of the halide solid electrolyte material is 1.14-1.67 mS/cm, and the specific discharge capacity at first cycle of 1C is 167-210 mAh/g.
In order to achieve the above object, another aspect of the present invention also provides a method for producing the above halide solid state electrolyte material, the method for producing the halide solid state electrolyte material comprising: mixing lithium halide, M halide, Y' halide, X-containing compound, solvent and optional hydrochloric acid and/or ammonium chloride, and reacting to obtain precursor-containing mixed solution, wherein the chemical formula of the precursor in the precursor-containing mixed solution is Li a M b Y ’ 1-b X c Cl a+4-b-c ·nH 2 O; drying the mixed solution containing the precursor to obtain a solid-phase productThe solid phase product has the chemical formula of Li a M b Y ’ 1-b X c Cl a+4-b-c ·mH 2 O, wherein m is any integer from 2 to 16 and n is more than m; and calcining the solid-phase product to obtain the halide solid electrolyte material.
Further, the method for producing a halide solid state electrolyte material further includes: carrying out vacuum heating treatment, rotary evaporation drying treatment, freeze drying treatment or microwave vacuum drying treatment on the precursor-containing mixed solution to obtain a solid-phase product; preferably, when the drying treatment is microwave vacuum drying treatment, the power of the microwave vacuum drying treatment is 400-2000W, the time is 4-18 h, and the vacuum degree is-0.1 MPa; when the drying treatment is vacuum heating treatment, the temperature of the vacuum heating treatment is 40-120 ℃, the heating rate is 0.1-5 ℃/min, the cooling rate is 0.5-5 ℃/min, the time is 4-24 h, and the vacuum degree is-0.1-0.5 MPa; when the drying treatment is rotary evaporation drying treatment, the temperature of the rotary evaporation drying treatment is 40-100 ℃, and the time is 4-16 h; when the drying treatment is freeze drying treatment, the temperature of the freeze drying treatment is-40 to-10 ℃, and the time is 6 to 24 hours.
Further, the calcination treatment is carried out under one or more conditions of vacuum, ar gas atmosphere and HCl gas atmosphere, the temperature of the calcination treatment is 100-500 ℃, the temperature rise rate is 0.1-5 ℃/min, and the time is 2-24 h; preferably, the temperature of the calcination treatment is 180-320 ℃, and the time is 3-12 h; preferably, the calcination treatment is performed under vacuum conditions and the degree of vacuum is-1 to 0.15MPa.
Further, the method for producing a halide solid state electrolyte material further comprises: sequentially calcining and powdering the solid-phase product to obtain a halide solid electrolyte material; preferably, the average particle size of the halide solid state electrolyte material is 0.2 to 20 μm.
Still another aspect of the present invention provides a lithium ion battery comprising a positive electrode layer, a negative electrode layer, and an electrolyte layer containing the above-described halide solid state electrolyte material provided herein, or a halide solid state electrolyte material produced by the above-described method for producing a halide solid state electrolyte material.
Further, lithium ion Chi Xuanzi is a semi-solid lithium ion battery or an all-solid lithium ion battery.
Compared with the traditional halide solid electrolyte material (such as Li) by applying the technical scheme of the invention 3 YbCl 6 、Li 3 InCl 6 ) The above Li provided by the present application a M b Y ’ 1-b X c Cl a+4-b-c Middle Y ’ The component partially replaces the original non-lithium metal component due to positive quadrivalent ions (such as Hf) in IVB group 4+ 、Zr 4+ 、Ti 4+ ) The halide solid electrolyte material has larger ionic radius, so that the interatomic gap in the microstructure of the halide solid electrolyte material is increased, and a good channel is provided for the migration of lithium ions; meanwhile, the compounding of the specific halogen can weaken the acting force with lithium elements, and the lithium ions can be conveniently transferred. The two effects can obviously improve the migration efficiency of lithium ions in the charging and discharging process, so that the ionic conductivity of the halide solid electrolyte material can be effectively improved.
Furthermore, li is added a M b Y ’ 1-b X c Cl a+4-b-c The content of each element component in the halide solid electrolyte material is controlled within the specific range (the value ranges of a, b and c are strictly limited), so that the synergistic effect among the element components can be fully exerted, the migration efficiency of lithium ions can be improved, and the conductivity of the halide solid electrolyte material can be further improved.
When the lithium ion conductive material is applied to a lithium ion battery, the lithium ion conductive phase interface resistance between a solid electrolyte and a positive electrode layer or a negative electrode layer can be reduced, the lithium ion transmission efficiency is favorably improved, and the electrochemical performance of the lithium ion battery is favorably improved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 shows Li prepared in example 1 of the present application 2.4 Yb 0.5 Hf 0.5 Br 2 Cl 3.9 An XRD pattern of the solid electrolyte material;
FIG. 2 shows Li obtained in comparative example 1 of the present application 3 YbCl 6 XRD pattern of solid state electrolyte material.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
As described in the background art, the existing halide solid state electrolyte materials have problems of poor crystallinity, low ionic conductivity, and poor stability. In order to solve the above technical problem, the present application provides a halide solid state electrolyte material having a chemical formula of Li a M b Y ’ 1-b X c Cl a+4-b-c Wherein M is a non-lithium metal ion, M includes but is not limited to one or more of the group consisting of Fe, al, ga, ho, yb, Y, sc, in and La series metal elements, and Y is ’ Including but not limited to one or more of the group IVB elements, X includes but is not limited to one or more of the group consisting of F, br and the group I element, and a is 0.5 to 3,b is 0.01 to 0.9 and c is 0.02 to 5.9.
Compared with the traditional halide solid electrolyte material (such as Li) 3 YbCl 6 、Li 3 InCl 6 ) The above-mentioned Li as provided in the present application a M b Y ’ 1-b X c Cl a+4-b-c Middle Y ’ The component partially replaces the original non-lithium metal component due to positive quadrivalent ions (such as Hf) in IVB group 4+ 、Zr 4+ 、Ti 4+ ) The halide solid electrolyte material has larger ionic radius, so that the interatomic gap in the microstructure of the halide solid electrolyte material is increased, and a good channel is provided for the migration of lithium ions; meanwhile, the compounding of specific halogen can weaken the acting force with lithium elements, and the lithium ions can be conveniently transferred. The two effects can obviously improve the migration efficiency of lithium ions in the charge and discharge process, thereby effectively improving halogenationIonic conductivity of the bulk solid state electrolyte material.
Furthermore, li is added a M b Y ’ 1-b X c Cl a+4-b-c The content of each element component in the halide solid electrolyte material is controlled within the specific range (the value ranges of a, b and c are strictly limited), so that the synergistic effect among the element components can be fully exerted, the migration efficiency of lithium ions can be improved, and the ionic conductivity of the halide solid electrolyte material can be further improved.
In a preferred embodiment, in the halide solid state electrolyte material, Y' includes, but is not limited to, one or more of the group consisting of Hf, zr, and Ti. The Y' element in the above kind is favorable for further improving the migration efficiency of lithium ions and further improving the ionic conductivity of the halide solid electrolyte material.
In a preferred embodiment, where M includes, but is not limited to Yb, or Ho, or a combination of Ho and Fe, Y' includes, but is not limited to Hf, or Zr, or a combination of Hf and Ti, and X includes, but is not limited to Br, or I, or a combination of Br and I. M, Y' and X include, but are not limited to, the above ranges, and limiting them to the above categories is advantageous for further improving the transfer efficiency of lithium ions and further improving the ionic conductivity of the halide solid state electrolyte material. Preferably, M is Yb, Y' is Hf, and X is Br; more preferably, M is Yb, Y' is Hf, X is Br and a is 1.1 to 2.8, b is 0.1 to 0.8 and c is 0.5 to 2.5; more preferably, a is 1.8 to 2.4, b is 0.1 to 0.8, and c is 0.8 to 2.5.
In a preferred embodiment, the halide solid state electrolyte material includes, but is not limited to, li 2.4 Yb 0.5 Hf 0.5 Br 2 Cl 3.9 、Li 2.1 Yb 0.4 Hf 0.6 Br 1.8 Cl 3.9 、Li 1.8 Yb 0.3 Hf 0.7 Br 1.5 Cl 4 、Li 2.1 Yb 0.5 Hf 0.5 Br 0.8 Cl 4.8 、Li 2.1 Yb 0.1 Hf 0.9 Br 2.5 Cl 3.5 、Li 2.4 Yb 0.6 Hf 0.4 Br 2.2 Cl 3.6 、Li 2.4 Yb 0.8 Hf 0.2 Br 1.6 Cl 4 、Li 2.8 Yb 0.88 Hf 0.12 Br 1.2 Cl 4.72 、Li 2.0 Yb 0.1 Hf 0.9 Br 0.8 Cl 5.1 Or Li 1.1 Yb 0.6 Hf 0.4 Br 0.5 Cl 4 。
In a preferred embodiment, the halide solid state electrolyte material is a glassy phase, a ceramic glassy phase, or a crystalline phase.
In a preferred embodiment, the halide solid state electrolyte material has an ionic conductivity of 1.14 to 1.67mS/cm and a specific first cycle discharge capacity of 167 to 210mAh/g at 1C.
The second aspect of the present application also provides a method for producing the above-described halide solid state electrolyte material, the method for producing the halide solid state electrolyte material including: mixing lithium halide, M halide, Y' halide, X-containing compound, solvent and optional hydrochloric acid and/or ammonium chloride, and reacting to obtain precursor-containing mixed solution, wherein the chemical formula of the precursor in the precursor-containing mixed solution is Li a M b Y ’ 1-b X c Cl a+4-b-c ·nH 2 O; drying the precursor-containing mixed solution to obtain a solid-phase product with the chemical formula of Li a M b Y ’ 1-b X c Cl a+4-b-c ·mH 2 O, wherein m is any integer from 2 to 16 and n is more than m; and calcining the solid-phase product to obtain the halide solid electrolyte material.
Mixing lithium halide, M halide and Y 'halide with a solvent, wherein in the reaction process, the lithium halide, the M halide and the Y' halide are dissolved in the solvent and are further aggregated to form precursor particles containing crystal water, and finally obtaining a precursor solution; the optional hydrochloric acid and/or ammonium chloride is added to inhibit the side reaction of hydrolysis of the reaction raw materials in a solvent (such as water), so that the generation rate of the precursor is improved. The solvent in the precursor-containing solution can be removed by drying the precursor-containing solution, so that a solid-phase product is obtained; the solid-phase product is calcined to enable the solid-phase product to generate dehydration reaction, and finally the halide solid-state electrolyte material is obtained.
The halide solid electrolyte Li can be obtained by adopting the preparation method of the halide solid electrolyte material a M b Y ’ 1-b X c Cl a+4-b-c Compared with the traditional halide solid electrolyte material (such as Li) 3 YbCl 6 、Li 3 InCl 6 ) The above Li provided by the present application a M b Y ’ 1-b X c Cl a+4-b-c Has high ion conductivity. By strictly limiting the amounts of the halides of lithium, M, Y' and X-containing compounds, li is added a M b Y ’ 1-b X c Cl a+4-b-c The content of each element component in the halide solid electrolyte material is controlled within a specific range, so that the migration efficiency of lithium ions is improved, and the ionic conductivity of the halide solid electrolyte material is further improved. When the lithium ion conductive coating is applied to a lithium ion battery, the lithium ion conductive phase interface resistance between a solid electrolyte and a positive electrode layer or a negative electrode layer can be reduced, the lithium ion transmission efficiency is favorably improved, and the electrochemical performance of the lithium ion battery is favorably improved.
In addition, compared with a solid-phase synthesis method, the liquid-phase synthesis method has the advantages of simple operation, short synthesis time, uniform particle size, lower cost and the like.
In a preferred embodiment, the solvent includes, but is not limited to, water and/or an organic solvent. The organic solvent includes, but is not limited to, one or more of ethanol, methanol, and acetone.
In order to further inhibit the hydrolysis side reaction of the reaction raw materials in the aqueous solution, thereby further improving the generation rate of the precursor, in a preferred embodiment, the weight percentage of the hydrochloric acid is 1 to 60wt% based on the total weight of the lithium halide, the M halide, the Y' halide and the X-containing compound. In another preferred embodiment, the ammonium chloride is present in an amount of 0.5 to 45 weight percent based on the total weight of the lithium halide, the halide of M, the halide of Y' and the compound comprising X. In yet another preferred embodiment, the hydrochloric acid and ammonium chloride are present in an amount of 0.5 to 60 weight percent based on the total weight of the lithium halide, the halide of M, the halide of Y', and the compound containing X.
The vacuum heating treatment can effectively reduce active impurities and gases in a vacuum heating device (such as a vacuum drying oven) through negative pressure, can remove oxygen and the like contacted with the surface of the material, inhibit the decomposition of the experimental material, and keep the drying of a vacuum condition heat treatment environment, thereby removing the solvent in the precursor-containing mixture. In the rotary evaporation drying treatment, the contact between the precursor-containing mixed liquid and impurities in the air is reduced, the evaporation area of the precursor-containing mixed liquid is increased under the rotary condition, the heating uniformity is improved, and the solvent removal rate of each part in the precursor-containing mixed liquid is the same. The freeze drying treatment utilizes the sublimation principle to ensure that the precursor-containing mixed solution is quickly frozen at low temperature under the vacuum condition, and the frozen solvent is directly sublimated and escaped, thereby obtaining a solid-phase product. The microwave vacuum drying treatment utilizes the dielectric loss principle to enable polar molecules (such as polar solvent) in a treated precursor-containing mixture to be subjected to orientation arrangement under the action of microwaves and to swing and collide sharply along with the change of an external electric field, so that a remarkable thermal effect is generated. Moreover, the above-mentioned action of the microwave is performed simultaneously inside and outside the precursor-containing mixture being treated, thereby forming a pressure gradient and a temperature gradient on the surface and inside thereof, thereby driving the solvent to flow toward the surface, and thus the microwave vacuum drying treatment has a faster drying speed.
In a preferred embodiment, the method for producing a halide solid state electrolyte material further comprises: and carrying out vacuum heating treatment, rotary evaporation drying treatment, freeze drying treatment or microwave vacuum drying treatment on the precursor-containing mixed solution to obtain a solid-phase product.
In a preferred embodiment, when the drying process is a microwave vacuum drying process, the power of the microwave vacuum drying process is 400-2000W, the time is 4-18 h, and the vacuum degree is-0.1 MPa, and the process parameters of the microwave vacuum drying process include, but are not limited to, the above ranges, which are favorable for controlling the solvent volatilization rate in the precursor-containing solution within a suitable range, so that the solvent is uniformly volatilized, a precursor with a higher crystallization degree is obtained, and good preconditions are provided for the subsequent calcination process. In the vacuum degree range, the higher the vacuum degree, the lower the boiling point of the solvent (such as water), so that the solvent is faster to migrate to the surface and easier to evaporate, thereby being beneficial to further improving the drying rate of the material.
When the drying treatment is vacuum heating treatment, the temperature of the vacuum heating treatment is 40-120 ℃, the temperature rising rate is 0.1-5 ℃/min, the temperature reducing rate is 0.5-5 ℃/min, the time is 4-24 h, and the vacuum degree is-0.1-0.5 MPa. The process parameters in the vacuum heating treatment process include, but are not limited to, the ranges, and limiting the process parameters in the ranges is beneficial to enabling the solvent volatilization rate in the precursor-containing solution to be more uniform, so that the precursor with higher crystallization degree is obtained, and good precondition is provided for the subsequent calcination treatment.
When the drying treatment is rotary evaporation drying treatment, the temperature of the rotary evaporation drying treatment is 40-100 ℃, and the time is 4-16 h. The process parameters in the rotary evaporation drying treatment process include, but are not limited to, the above ranges, and limiting the process parameters in the above ranges is beneficial to controlling the solvent volatilization rate in the precursor-containing solution to be in an appropriate range, so that the solvent is uniformly volatilized, the precursor with higher crystallization degree is obtained, and good precondition is provided for the subsequent calcination treatment.
When the drying treatment is freeze drying treatment, the temperature of the freeze drying treatment is-40 to-10 ℃, and the time is 6 to 24 hours. The temperature and time of the freeze-drying process include, but are not limited to, the above ranges, and the limitation of the temperature and time within the above ranges is beneficial for controlling the solvent volatilization rate in the precursor-containing solution within a suitable range, so that the solvent is uniformly volatilized, a precursor with higher crystallization degree is obtained, and good precondition is provided for the subsequent calcination process.
Impurities (e.g., M-O-Cl impurities) are easily formed during the calcination treatment of the solid phase product, which may lead to non-uniform conductivity properties at various locations in the resulting halide electrolyte material and may also lead to a decrease in its conductivity. In a preferred embodiment, the calcination treatment is carried out under one or more conditions of vacuum, ar gas atmosphere and HCl gas atmosphere, the temperature of the calcination treatment is 100-500 ℃, the temperature rise rate is 0.1-5 ℃/min, and the time is 2-24 h. Compared with the method of directly carrying out calcination treatment in the air, the adoption of the calcination treatment in the specific conditions is beneficial to reducing the impurity content in the prepared halide solid electrolyte material and further is beneficial to improving the conductivity of the halide electrolyte material; meanwhile, the temperature, time and heating rate of the calcination treatment are limited in the ranges, so that the purity of the crystal form of the prepared halide solid electrolyte material is improved, the quality of the product during batch synthesis is improved, the ionic conductivity of the product is further exerted, and the electrochemical performance of the lithium ion battery is further improved.
In order to further improve the purity of the crystal form of the halide solid electrolyte material, further exert the ionic conductivity of the halide solid electrolyte material and further improve the electrochemical performance of the lithium ion battery, the calcination treatment temperature is preferably 180-320 ℃, and the calcination treatment time is preferably 3-12 hours.
In order to further improve the purity of the crystal form of the halide solid electrolyte material, reduce the content of impurities, further exert the ion conductivity of the halide solid electrolyte material and further improve the electrochemical performance of the lithium ion battery, preferably, the calcination treatment is carried out under a vacuum condition, and the vacuum degree is-1 to 0.15MPa.
In a preferred embodiment, the method for producing a halide solid state electrolyte material further comprises: and sequentially calcining and powdering the solid-phase product to obtain the halide solid electrolyte material. The powdering treatment of the product obtained after the solid-phase product is calcined is beneficial to making the particle size of the prepared halide solid electrolyte material more uniform.
It is preferable that the average particle size of the halide solid state electrolyte material is 0.2 to 20 μm in order to reduce the interface resistance and facilitate the application thereof to a lithium ion battery, because an excessive average particle size of the halide solid state electrolyte material may cause an increase in the interface resistance during the application thereof.
The third aspect of the present application also provides a lithium ion battery comprising a positive electrode layer, a negative electrode layer, and an electrolyte layer, wherein the electrolyte layer comprises the above-mentioned halide solid state electrolyte material provided by the present application, or the halide solid state electrolyte material prepared by the above-mentioned method for preparing a halide solid state electrolyte material.
The halide solid electrolyte material has high ionic conductivity and stability, and is applied to a lithium ion battery, so that the reduction of the lithium ion conduction phase interface resistance between the solid electrolyte and the positive electrode layer or the negative electrode layer is facilitated, the improvement of the lithium ion transmission efficiency is facilitated, and the improvement of the electrochemical performance of the lithium ion battery is further facilitated.
In a preferred embodiment, the lithium ion battery includes, but is not limited to, a semi-solid lithium ion battery or an all-solid lithium ion battery.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
A method of preparing a solid state electrolyte material, comprising:
(1) Weighing 0.4mol LiCl and 0.5mol YbCl in an argon atmosphere 3 、0.5mol HfCl 4 2mol of LiBr, and mixing the weighed raw materials with a solvent (hydrochloric acid aqueous solution) while stirring, wherein the stirring speed is 600rpm/min, and reacting for 8 hours to obtain a precursor-containing mixed solution;
(2) Carrying out microwave vacuum drying treatment on the mixed solution containing the precursor, setting the power of intelligent microwave vacuum low-temperature drying equipment to be 800W and the vacuum degree to be-0.095 MPa, and treating for 8h to obtain a solid-phase product; the solid phase product has the chemical formula of Li 2.4 Yb 0.5 Hf 0.5 Br 2 Cl 3.9 ·2H 2 O；
(3) Calcining the solid-phase product under vacuum condition (vacuum degree of 0.1 MPa), heating to 200 ℃ at a heating rate of 2 ℃/min, and calcining for 4h to obtain a calcined solid-phase product;
(4) Grinding the calcined solid-phase product to obtain Li 2.4 Yb 0.5 Hf 0.5 Br 2 Cl 3.9 Solid state electricityA material is decomposed.
FIG. 1 shows Li prepared in example 1 of the present application 2.4 Yb 0.5 Hf 0.5 Br 2 Cl 3.9 As can be seen from FIG. 1, the XRD pattern of the solid electrolyte material has strong peak intensity, obvious characteristic peak and high crystal purity.
Example 2
The difference from example 1 is that: the drying process is different.
A method of preparing a solid state electrolyte material, comprising:
(1) Obtaining a precursor-containing mixed solution in the same manner as in the step (1) in example 1;
(2) Transferring the precursor-containing mixed solution into a vacuum drying oven for vacuum drying treatment, setting the temperature of the vacuum drying oven at 80 ℃, the heating rate at 5 ℃/min and the vacuum degree at 0.1MPa, after treating for 8h, cooling to room temperature at the cooling rate of 5 ℃/min to obtain a precursor Li 2.4 Yb 0.5 Hf 0.5 Br 2 Cl 3.9 ·2H 2 O；
(3) The same procedure as in step (3) in example 1 gave a solid-phase product after calcination;
(4) Grinding the calcined solid-phase product to obtain Li 2.4 Yb 0.5 Hf 0.5 Br 2 Cl 3.9 Solid electrolyte material (average particle size 2.1 μm).
Example 3
The difference from example 1 is that: the drying process is different.
A method of preparing a solid state electrolyte material, comprising:
(1) Obtaining a precursor-containing mixed solution in the same manner as in the step (1) in example 1;
(2) Transferring the precursor-containing mixed solution to a rotary evaporator for drying, setting the temperature of the rotary evaporator to be 80 ℃, and treating for 8h to obtain a precursor Li 2.4 Yb 0.5 Hf 0.5 Br 2 Cl 3.9 ·2H 2 O；
(3) The same procedure as in step (3) in example 1 gave a solid-phase product after calcination;
(4) Grinding the calcined solid-phase product to obtain Li 2.4 Yb 0.5 Hf 0.5 Br 2 Cl 3.9 Solid electrolyte material (average particle size 1.8 μm).
Example 4
The difference from example 1 is that: the drying process is different.
A method of preparing a solid state electrolyte material, comprising:
(1) Obtaining a precursor-containing mixed solution in the same manner as in the step (1) in example 1;
(2) Transferring the precursor-containing mixed solution into a freeze vacuum drying oven for freeze drying, setting the temperature of the freeze vacuum drying oven at-10 ℃ and the vacuum degree at 0.1MPa, and treating for 8h to obtain a precursor Li 2.4 Yb 0.5 Hf 0.5 Br 2 Cl 3.9 ·2H 2 O；
(3) The same procedure as in step (3) in example 1 gave a solid-phase product after calcination;
(4) Grinding the calcined solid-phase product to obtain Li 2.4 Yb 0.5 Hf 0.5 Br 2 Cl 3.9 Solid electrolyte material (average particle size 2.1 μm).
Example 5
The difference from example 1 is that: in the step (1), the raw materials are weighed in different amounts.
A method of preparing a solid state electrolyte material, comprising:
(1) Weighing 0.3mol LiCl and 0.4mol YbCl in an argon atmosphere 3 、0.6mol HfCl 4 Mixing the weighed raw materials with a solvent (same as in example 1) while stirring, wherein the stirring speed is 600rpm/min, and obtaining a precursor-containing mixed solution after reacting for 8 hours;
(2) The same procedure as in step (2) of example 1 was repeated to obtain a solid-phase product; the solid phase product has the chemical formula of Li 2.1 Yb 0.4 Hf 0.6 Br 1.8 Cl 3.9 ·2H 2 O；
(3) The same procedure as in step (3) in example 1 gave a solid-phase product after calcination;
(4) In the same manner as in the step (4) in example 1, li was obtained 2.1 Yb 0.4 Hf 0.6 Br 1.8 Cl 3.9 Solid electrolyte material (average particle size 2.3 μm).
Example 6
The difference from example 1 is that: in the step (1), the raw materials are weighed in different amounts.
A method of producing a solid state electrolyte material, comprising:
(1) Weighing 0.3mol LiCl and 0.3mol YbCl in an argon atmosphere 3 、0.7mol HfCl 4 Mixing the weighed raw materials with a solvent (same as in example 1) while stirring, wherein the stirring speed is 600rpm/min, and obtaining a precursor-containing mixed solution after reacting for 8 hours;
(2) The same procedure as in step (2) in example 1 gave a solid-phase product; the solid phase product has the chemical formula of Li 1.8 Yb 0.3 Hf 0.7 Br 1.5 Cl 4 ·2H 2 O；
(3) The same procedure as in step (3) in example 1 gave a solid-phase product after calcination;
(4) In the same manner as in the step (4) in example 1, li was obtained 1.8 Yb 0.3 Hf 0.7 Br 1.5 Cl 4 Solid electrolyte material (average particle size 2.2 μm).
Example 7
The difference from example 1 is that: in the step (1), the raw materials are weighed in different amounts.
A method of preparing a solid state electrolyte material, comprising:
(1) In an argon atmosphere, 1.3mol LiCl and 0.5mol YbCl are weighed 3 、0.5mol HfCl 4 0.8mol of LiBr, and mixing the weighed raw materials with a solvent (same as in example 1) while stirring, wherein the stirring speed is 600rpm/min, and obtaining a precursor-containing mixed solution after reacting for 8 hours;
(2) The same procedure as in step (2) in example 1 gave a solid-phase product; the solid phase product has the chemical formula of Li 2.1 Yb 0.5 Hf 0.5 Br 0.8 Cl 4.8 2H 2 O；
(3) The same procedure as in step (3) in example 1 gave a solid-phase product after calcination;
(4) In the same manner as in the step (4) in example 1, li was obtained 2.1 Yb 0.5 Hf 0.5 Br 0.8 Cl 4.8 Solid electrolyte material (average particle size 2.3 μm).
Example 8
The difference from example 1 is that: in the step (1), the raw materials are weighed in different amounts.
A method of preparing a solid state electrolyte material, comprising:
(1) Weighing 0.1mol of YbBr in an argon atmosphere 3 、0.6mol HfCl 4 、0.3mol HfBr 4 2.1mol of LiBr, and mixing the weighed raw materials with a solvent (same as in example 1) while stirring, wherein the stirring speed is 600rpm/min, and obtaining a precursor-containing mixed solution after reacting for 8 hours;
(2) The same procedure as in step (2) in example 1 gave a solid-phase product; the solid phase product has the chemical formula of Li 2.1 Yb 0.1 Hf 0.9 Br 2.5 Cl 3.5 ·2H 2 O；
(3) The same procedure as in step (3) in example 1 gave a solid-phase product after calcination;
(4) In the same manner as in the step (4) in example 1, li was obtained 2.1 Yb 0.1 Hf 0.9 Br 2.5 Cl 3.5 Solid electrolyte material (average particle size 2.6 μm).
Example 9
The difference from example 1 is that: in the step (1), the raw materials are weighed in different amounts.
A method of preparing a solid state electrolyte material, comprising:
(1) Weighing 0.2LiCl and 0.6mol YbCl in an argon atmosphere 3 、0.4mol HfCl 4 2.2mol of LiBr, and mixing the weighed raw materials with a solvent (same as in example 1) while stirring, wherein the stirring speed is 600rpm/min, and obtaining a precursor-containing mixed solution after reacting for 8 hours;
(2) The same procedure as in step (2) in example 1 gave a solid-phase product; the solid phase product has the chemical formula of Li 2.4 Yb 0.6 Hf 0.4 Br 2.2 Cl 3.6 ·2H 2 O；
(3) The same procedure as in step (3) in example 1 gave a solid-phase product after calcination;
(4) In the same manner as in the step (4) in example 1, li was obtained 2.4 Yb 0.6 Hf 0.4 Br 2.2 Cl 3.6 Solid electrolyte material (average particle size 2.5 μm).
Example 10
The difference from example 1 is that: in the step (1), the raw materials are weighed in different amounts.
A method of preparing a solid state electrolyte material, comprising:
(1) Weighing 0.8mol LiCl and 0.8mol YbCl in an argon atmosphere 3 、0.2mol HfCl 4 Mixing the weighed raw materials with a solvent (same as in example 1) while stirring, wherein the stirring speed is 600rpm/min, and obtaining a precursor-containing mixed solution after reacting for 8 hours;
(2) The same procedure as in step (2) in example 1 gave a solid-phase product; the solid phase product has the chemical formula of Li 2.4 Yb 0.8 Hf 0.2 Br 1.6 Cl 4 ·2H 2 O；
(3) The same procedure as in step (3) in example 1 gave a solid-phase product after calcination;
(4) In the same manner as in the step (4) in example 1, li was obtained 2.4 Yb 0.8 Hf 0.2 Br 1.6 Cl 4 Solid electrolyte material (average particle size 2.7 μm).
Example 11
The difference from example 1 is that: in the step (1), the raw materials are weighed in different amounts.
A method of preparing a solid state electrolyte material, comprising:
(1) Weighing 1.6mol LiCl and 0.88mol YbCl in an argon atmosphere 3 、0.12mol HfCl 4 1.2mol of LiBr, and stirring the weighed raw materials and the LiBrMixing the solvent (same as the example 1), wherein the stirring speed is 600rpm/min, and reacting for 8 hours to obtain a precursor-containing mixed solution;
(2) The same procedure as in step (2) in example 1 gave a solid-phase product; the solid phase product has the chemical formula of Li 2.8 Yb 0.88 Hf 0.12 Br 1.2 Cl 4.72 ·2H 2 O；
(3) The same procedure as in step (3) in example 1 gave a solid-phase product after calcination;
(4) In the same manner as in the step (4) in example 1, li was obtained 2.8 Yb 0.88 Hf 0.12 Br 1.2 Cl 4.72 Solid electrolyte material (average particle size 2.3 μm).
Example 12
The difference from example 1 is that: in the step (1), the raw materials are weighed in different amounts.
A method of preparing a solid state electrolyte material, comprising:
(1) Weighing 1.4mol LiCl and 0.1mol YbCl in an argon atmosphere 3 、0.9mol HfCl 4 0.6mol of LiBr, and mixing the weighed raw materials with a solvent (same as in example 1) while stirring, wherein the stirring speed is 600rpm/min, and obtaining a precursor-containing mixed solution after reacting for 8 hours;
(2) The same procedure as in step (2) in example 1 gave a solid-phase product; the solid phase product has the chemical formula of Li 2.0 Yb 0.1 Hf 0.9 Br 0.8 Cl 5.1 ·2H 2 O；
(3) The same procedure as in step (3) in example 1 gave a solid-phase product after calcination;
(4) In the same manner as in the step (4) in example 1, li was obtained 2.0 Yb 0.1 Hf 0.9 Br 0.8 Cl 5.1 Solid electrolyte material (average particle size 2.1 μm).
Example 13
The difference from example 1 is that: in the step (1), the raw materials are weighed in different amounts.
A method of preparing a solid state electrolyte material, comprising:
(1) Weighing 0.6mol LiCl and 0.6mol YbCl in an argon atmosphere 3 、0.4mol HfCl 4 0.5mol of LiBr, and mixing the weighed raw materials with a solvent (same as in example 1) while stirring, wherein the stirring speed is 600rpm/min, and obtaining a precursor-containing mixed solution after reacting for 8 hours;
(2) The same procedure as in step (2) in example 1 gave a solid-phase product; the solid phase product has the chemical formula of Li 1.1 Yb 0.6 Hf 0.4 Br 0.5 Cl 4 ·2H 2 O；
(3) The same procedure as in step (3) in example 1 gave a solid-phase product after calcination;
(4) In the same manner as in the step (4) in example 1, li was obtained 1.1 Yb 0.6 Hf 0.4 Br 0.5 Cl 4 Solid electrolyte material (average particle size 2.8 μm).
Example 14
The difference from example 1 is that: changing the dosage proportion of the raw materials in the step (1) to ensure that the molar ratio of Li, yb, hf and Br elements is 0.5. Finally obtaining Li 0.5 Yb 0.01 Hf 0.99 Br 0.02 Cl 4.4 A solid electrolyte material.
Example 15
The difference from example 1 is that: the proportion of the raw materials in the step (1) is changed so that the molar ratio of Li, yb, hf and Br elements is 2.0. Finally obtaining Li 2.0 Yb 0.01 Hf 0.99 Br 2.9 Cl 3.09 A solid electrolyte material.
Example 16
The difference from example 1 is that: the power of the microwave vacuum drying treatment is 400W, the time is 18h, and the vacuum degree is-0.1 MPa.
Example 17
The difference from example 1 is that: the power of the microwave vacuum drying treatment is 2000W, the time is 4h, and the vacuum degree is 0.1MPa.
Example 18
The difference from example 1 is that: the power of the microwave vacuum drying treatment is 2500W, the time is 2h, and the vacuum degree is 0.15MPa.
Example 19
The difference from example 3 is that: the temperature of the rotary evaporation drying treatment is 40 ℃, and the time is 16h.
Example 20
The difference from example 3 is that: the temperature of the rotary evaporation drying treatment is 120 ℃, and the time is 4h.
Example 21
The difference from example 3 is that: the temperature of the rotary evaporation drying treatment is 60 ℃, and the time is 3h.
Example 22
The difference from example 1 is that: the temperature of the calcination treatment is 100 ℃, the heating rate is 0.1 ℃/min, and the time is 24h.
Example 23
The difference from example 1 is that: the temperature of the calcination treatment is 500 ℃, the heating rate is 5 ℃/min, and the time is 2h.
Example 24
The difference from example 1 is that: the temperature of the calcination treatment is 550 ℃, the heating rate is 10 ℃/min, and the time is 1.5h.
Example 25
The difference from example 1 is that: the temperature of the calcination treatment is 180 ℃ and the time is 12h.
Example 26
The difference from example 1 is that: the temperature of the calcination treatment was 320 ℃ and the time was 3 hours.
Example 27
The difference from example 1 is that: in the step (1), the types of the weighed raw materials are different.
A method of preparing a solid state electrolyte material, comprising:
(1) Weighing 0.4mol LiCl and 0.2mol YbCl in an argon atmosphere 3 、0.3mol HoCl 3 、0.5mol HfCl 4 2mol of LiBr, and mixing the weighed raw materials with a solvent (same as in example 1) while stirring, wherein the stirring speed is 600rpm/min, and obtaining a precursor-containing mixed solution after reacting for 8 hours;
(2) With fruitThe same procedure as in step (2) of example 1 gave a solid product; the solid phase product has the chemical formula of Li 2.4 Yb 0.2 Ho 0.3 Hf 0.5 Br 2 Cl 3.4 ·2H 2 O；
(3) The same procedure as in step (3) in example 1 gave a solid-phase product after calcination;
(4) In the same manner as in the step (4) in example 1, li was obtained 2.4 Yb 0.5 Ho 0.5 Hf 0.5 Br 2 Cl 3.9 Solid electrolyte material (average particle size 2.4 μm).
Example 28
The difference from example 1 is that: in the step (1), the types of the weighed raw materials are different.
A method of preparing a solid state electrolyte material, comprising:
(1) In an argon atmosphere, 0.3mol of LiCl and 0.5mol of HoCl are weighed 3 、0.5mol HfCl 4 Mixing the weighed raw materials with a solvent (same as in example 1) while stirring, wherein the stirring speed is 600rpm/min, and obtaining a precursor-containing mixed solution after reacting for 8 hours;
(2) The same procedure as in step (2) in example 1 gave a solid-phase product; the solid phase product has the chemical formula of Li 1.8 Ho 0.5 Hf 0.5 Br 1.5 Cl 3.8 ·2H 2 O；
(3) The same procedure as in step (3) in example 1 was repeated to obtain a calcined solid-phase product;
(4) In the same manner as in step (4) in example 1, li was obtained 1.8 Ho 0.5 Hf 0.5 Br 2.5 Cl 3.8 Solid electrolyte material (average particle size 3.1 μm).
Comparative example 1
A method of producing a solid state electrolyte material, comprising:
(1) Weighing 3mol LiCl and 1mol YbCl in an argon atmosphere 3 Mixing the weighed raw materials with a solvent (hydrochloric acid aqueous solution) while stirring, wherein the stirring speed is 600rpm/min, and reacting for 8 hours to obtain a precursor-containing mixed solution;
(2) Carrying out microwave vacuum drying treatment on the mixed solution containing the precursor, setting the power of intelligent microwave vacuum low-temperature drying equipment to be 800W and the vacuum degree to be-0.095 MPa, and treating for 8h to obtain a solid-phase product; the solid phase product has the chemical formula of Li 3 YbCl 6 ·2H 2 O；
(3) Calcining the solid-phase product under the vacuum condition that the vacuum degree is 0.1MPa, heating to 200 ℃ at the heating rate of 2 ℃/min, and calcining for 4 hours to obtain a calcined solid-phase product;
(4) Grinding the calcined solid-phase product to obtain Li 3 YbCl 6 The average particle diameter of the solid electrolyte material was measured to be 2.5 μm.
FIG. 2 shows Li prepared in comparative example 1 3 YbCl 6 XRD pattern of solid state electrolyte material. In FIG. 2Li 3 YbCl 6 Lower peak intensity than example 1, indicating that the Li prepared in comparative example 1 3 YbCl 6 Is less crystalline.
Comparative example 2
The difference from example 1 is that: changing the dosage proportion of the raw materials in the step (1) to ensure that the molar ratio of Li, yb, hf and Br elements is 3.1. Finally obtaining Li 3.1 Yb 0.95 Hf 0.05 Br 0.01 Cl 6.14 A solid electrolyte material.
The halide solid state electrolyte materials prepared in all the above examples and comparative examples of the present application were subjected to impedance analysis to obtain ionic conductivity (mS/cm) according to the following specific procedures: 100mg of halide solid electrolyte material was weighed and placed in a die sleeve, pressurized (100 Pa ready for forming a pellet, and subjected to AC impedance spectroscopy using an impedance analyzer, and the ionic conductivity was calculated from the impedance values, with the test results shown in Table 1.
All the halide solid electrolyte materials prepared in all the examples and comparative examples of the present application were assembled into an all-solid lithium ion battery, and the charge and discharge properties thereof were tested. The assembly process of the all-solid-state lithium ion battery is as follows: (1) In an argon glove box, the prepared halide solid electrolyte material and the positive electrode active material are weighed according to the weight ratio of 20Li(Ni 0.8 Co 0.1 Mn 0.1 )O 2 (NCM 811), and grinding uniformly to obtain a composite cathode material; (2) Putting 12mg of the composite anode material into a mold sleeve, laminating the composite anode material with 60mg of halide solid electrolyte material, and performing pressure molding to obtain a solid electrolyte layer; (3) Laminating an aluminum foil layer on one side of the positive electrode, laminating an indium sheet (negative electrode layer) on the opposite side of the solid electrolyte layer in contact with the positive electrode, and applying pressure to obtain a laminated body with a structure of composite positive electrode layer/solid electrolyte layer/negative electrode layer; (4) Stainless steel current collectors were provided on the upper and lower surfaces of the laminate, and current collecting leads were provided, to obtain an all-solid-state lithium ion battery.
The halide solid electrolyte materials prepared in all the examples and comparative examples described above in the present application were subjected to a specific discharge capacity test at a discharge rate of 1C, and the measured specific first cycle discharge capacity is shown in table 1.
TABLE 1
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects:
as can be seen from comparison of examples 1, 2, 3 and 4, of the above four drying methods, the ionic conductivity of the final halide solid electrolyte material obtained by the microwave vacuum drying treatment and the first cycle specific discharge capacity of the lithium ion battery obtained were the best.
Comparing examples 1, 5 to 15, 27 and 28 and comparative examples 1 and 2, it can be seen that Li is added a M b Y ’ 1-b X c Cl a+4-b-c The content of each element component in the halide solid electrolyte material is controlled within a specific range (the dosage of lithium halide, M halide, Y' halide and X-containing compound is strictly limited so as to strictly limit the value range of a, b and c), so that the synergistic effect among the element components is fully exerted, the migration efficiency of lithium ions is improved, and the ionic conductivity of the halide solid electrolyte material is further improved.
As can be seen from a comparison of FIGS. 1 and 2, the present invention was carried outExample 1 produced halide solid electrolyte material Li 2.4 Yb 0.5 Hf 0.5 Br 2 Cl 3.9 Li without any doping and modification, obtained in comparative example 1 3 YbCl 6 Have the same crystal form. As can be seen from FIG. 1, li 2.4 Yb 0.5 Hf 0.5 Br 2 Cl 3.9 The peak intensity of the halide solid electrolyte material is strong, and the characteristic peak is obvious and complete, which shows that the halide solid electrolyte material prepared by the application has high crystallization degree; while Li in FIG. 2 3 YbCl 6 Lower peak intensity, indicating that Li prepared in comparative example 1 3 YbCl 6 Is less crystalline.
Comparing examples 1 and 16 to 18, it can be seen that the process parameters of the microwave vacuum drying process include, but are not limited to, the preferred ranges of the present application, and it is advantageous to control the solvent evaporation rate in the precursor-containing solution within the preferred ranges of the present application, so that the solvent is uniformly evaporated, and a precursor with a higher degree of crystallization is obtained, which provides good precondition for the subsequent calcination process.
Comparing examples 3 and 19 to 21, it can be seen that the process parameters in the rotary evaporation drying process include, but are not limited to, the preferred ranges of the present application, and it is advantageous to control the solvent evaporation rate in the precursor-containing solution within the preferred ranges of the present application, so that the solvent is uniformly evaporated to obtain a precursor with higher crystallinity, and good precondition is provided for the subsequent calcination process.
It is understood from comparative examples 1, 22 to 24 that limiting the temperature, time, and rate of temperature rise of the calcination treatment to the preferable ranges of the present application is advantageous to increase the produced halide solid electrolyte material Li as compared with other ranges 2.4 Yb 0.5 Hf 0.5 Br 2 Cl 3.9 The purity of the crystal form improves the quality of the product during batch synthesis, and further exerts the ionic conductivity of the product, and further improves the electrochemical performance of the lithium ion battery.
As can be seen by comparing examples 1, 25 and 26, the temperature, time and rate of temperature rise of the calcination treatment were further limited as compared with other rangesIs favorable for further improving the halide solid electrolyte material Li in the preferable range of the application 2.4 Yb 0.5 Hf 0.5 Br 2 Cl 3.9 The purity of the crystal form further exerts the ionic conductivity of the crystal form, and further improves the electrochemical performance of the lithium ion battery.
It is noted that the terms first, second and the like in the description and in the claims of the present application are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances such that the embodiments of the application described herein are, for example, capable of operation in sequences other than those described or illustrated herein.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A halide solid state electrolyte material characterized in that the chemical formula of the halide solid state electrolyte material is Li a M b Y’ 1-b X c Cl a+4-b-c Wherein M is non-lithium metal ion, M is selected from one or more of the group consisting of Fe, al, ga, ho, yb, Y, sc, in and La series metal elements, Y' is selected from one or more of IVB group elements, X is selected from one or more of the group consisting of F, br and I element, a is 0.5-3,b and is 0.01-0.9, and c is 0.02-5.9.
2. The halide solid state electrolyte material according to claim 1, wherein in the halide solid state electrolyte material, the Y' is one or more selected from the group consisting of Hf, zr, and Ti.
3. The halide solid state electrolyte material of claim 1 or 2, wherein when M is selected from Yb, or Ho, or a combination of Ho and Fe, Y' is selected from Hf, or Zr, or a combination of Hf and Ti, and X is selected from Br, or I, or a combination of Br and I;
preferably, said M is Yb, said Y' is Hf, and said X is Br;
more preferably, said M is Yb, said Y' is Hf, said X is Br and said a is 1.1 to 2.8, said b is 0.1 to 0.88 and said c is 0.5 to 2.5; more preferably, a is 1.8 to 2.4, b is 0.1 to 0.8, and c is 0.8 to 2.5.
4. The halide solid state electrolyte material according to claim 1 or 2, wherein the halide solid state electrolyte material is selected from Li 2.4 Yb 0.5 Hf 0.5 Br 2 Cl 3.9 、Li 2.1 Yb 0.4 Hf 0.6 Br 1.8 Cl 3.9 、Li 1.8 Yb 0.3 Hf 0.7 Br 1.5 Cl 4 、Li 2.1 Yb 0.5 Hf 0.5 Br 0.8 Cl 4.8 、Li 2.1 Yb 0.1 Hf 0.9 Br 2.5 Cl 3.5 、Li 2.4 Yb 0.6 Hf 0.4 Br 2.2 Cl 3.6 、Li 2.4 Yb 0.8 Hf 0.2 Br 1.6 Cl 4 、Li 2.8 Yb 0.88 Hf 0.12 Br 1.2 Cl 4.72 、Li 2.0 Yb 0.1 Hf 0.9 Br 0.8 Cl 5.1 Or Li 1.1 Yb 0.6 Hf 0.4 Br 0.5 Cl 4 。
5. The halide solid state electrolyte material according to claim 1 or 2, wherein the halide solid state electrolyte material is a glass phase, a ceramic glass phase, or a crystalline phase;
preferably, the ionic conductivity of the halide solid electrolyte material is 1.14-1.67 mS/cm, and the specific first-cycle discharge capacity of 1C is 167-210 mAh/g.
6. A production method of a halide solid state electrolyte material according to any one of claims 1 to 5, characterized in that the production method of a halide solid state electrolyte material comprises:
mixing lithium halide, M halide, Y' halide, X-containing compound, solvent and optional hydrochloric acid and/or ammonium chloride, and reacting to obtain precursor-containing mixed solution, wherein the chemical formula of a precursor in the precursor-containing mixed solution is Li a M b Y’ 1- b X c Cl a+4-b-c ·nH 2 O；
Drying the precursor-containing mixed solution to obtain a solid-phase product, wherein the chemical formula of the solid-phase product is Li a M b Y’ 1-b X c Cl a+4-b-c ·mH 2 O, wherein m is any integer from 2 to 16 and n > m;
and calcining the solid-phase product to obtain the halide solid-state electrolyte material.
7. The method of producing a halide solid state electrolyte material according to claim 6, further comprising:
carrying out vacuum heating treatment, rotary evaporation drying treatment, freeze drying treatment or microwave vacuum drying treatment on the precursor-containing mixed solution to obtain a solid-phase product;
preferably, when the drying treatment is microwave vacuum drying treatment, the power of the microwave vacuum drying treatment is 400-2000W, the time is 4-18 h, and the vacuum degree is-0.1 MPa;
when the drying treatment is vacuum heating treatment, the temperature of the vacuum heating treatment is 40-120 ℃, the heating rate is 0.1-5 ℃/min, the cooling rate is 0.5-5 ℃/min, the time is 4-24 h, and the vacuum degree is-0.1-0.5 MPa;
when the drying treatment is rotary evaporation drying treatment, the temperature of the rotary evaporation drying treatment is 40-100 ℃, and the time is 4-16 h;
when the drying treatment is freeze drying treatment, the temperature of the freeze drying treatment is-40 to-10 ℃, and the time is 6 to 24 hours.
8. The method for producing a halide solid electrolyte material according to claim 7, wherein the calcination treatment is performed in one or more conditions selected from a vacuum atmosphere, an Ar gas atmosphere, and an HCl gas atmosphere, and the calcination treatment is performed at a temperature of 100 to 500 ℃, at a temperature increase rate of 0.1 to 5 ℃/min, and for a time of 2 to 24 hours;
preferably, the temperature of the calcination treatment is 180-320 ℃, and the time is 3-12 h;
preferably, the calcination treatment is performed under the vacuum condition, and the vacuum degree is-10 to 0.15MPa.
9. The method of producing a halide solid state electrolyte material according to claim 8, further comprising:
sequentially carrying out the calcination treatment and the powdering treatment on the solid-phase product to obtain the halide solid-state electrolyte material;
preferably, the average particle size of the halide solid state electrolyte material is 0.2 to 20 μm.
10. A lithium ion battery comprising a positive electrode layer, a negative electrode layer and an electrolyte layer, characterized in that the electrolyte layer contains the halide solid state electrolyte material of any one of claims 1 to 5, or the halide solid state electrolyte material produced by the production method of the halide solid state electrolyte material of any one of claims 6 to 9;
preferably, the lithium ion Chi Xuanzi is a semi-solid lithium ion battery or an all-solid lithium ion battery.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116799294A (en) * | 2023-08-16 | 2023-09-22 | 有研(广东)新材料技术研究院 | Inorganic solid electrolyte material with high fluorine content and preparation and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159320A (en) * | 2016-08-23 | 2016-11-23 | 洁能电投（北京）新能源科技有限公司 | A kind of modified LAGP solid electrolyte material and preparation method thereof |
| CN110970667A (en) * | 2019-12-20 | 2020-04-07 | 横店集团东磁股份有限公司 | Composite halide solid electrolyte, preparation method and application thereof |
| CN113889662A (en) * | 2021-09-29 | 2022-01-04 | 蜂巢能源科技有限公司 | Halide solid electrolyte material and preparation method and application thereof |
| CN113991167A (en) * | 2021-10-26 | 2022-01-28 | 西安交通大学 | Halide solid electrolyte material and preparation method and application thereof |
| CN114335681A (en) * | 2021-11-29 | 2022-04-12 | 蜂巢能源科技(无锡)有限公司 | Inorganic halide solid electrolyte, preparation method thereof, lithium ion battery and application |
| CN114865068A (en) * | 2022-05-18 | 2022-08-05 | 深圳大学 | Iron-based lanthanum lithium zirconate solid electrolyte, preparation method thereof and lithium battery |
| WO2022180980A1 (en) * | 2021-02-26 | 2022-09-01 | パナソニックＩｐマネジメント株式会社 | Solid electrolyte material and battery using same |
-
2022
- 2022-11-28 CN CN202211502486.XA patent/CN115732751A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159320A (en) * | 2016-08-23 | 2016-11-23 | 洁能电投（北京）新能源科技有限公司 | A kind of modified LAGP solid electrolyte material and preparation method thereof |
| CN110970667A (en) * | 2019-12-20 | 2020-04-07 | 横店集团东磁股份有限公司 | Composite halide solid electrolyte, preparation method and application thereof |
| WO2022180980A1 (en) * | 2021-02-26 | 2022-09-01 | パナソニックＩｐマネジメント株式会社 | Solid electrolyte material and battery using same |
| CN113889662A (en) * | 2021-09-29 | 2022-01-04 | 蜂巢能源科技有限公司 | Halide solid electrolyte material and preparation method and application thereof |
| CN113991167A (en) * | 2021-10-26 | 2022-01-28 | 西安交通大学 | Halide solid electrolyte material and preparation method and application thereof |
| CN114335681A (en) * | 2021-11-29 | 2022-04-12 | 蜂巢能源科技(无锡)有限公司 | Inorganic halide solid electrolyte, preparation method thereof, lithium ion battery and application |
| CN114865068A (en) * | 2022-05-18 | 2022-08-05 | 深圳大学 | Iron-based lanthanum lithium zirconate solid electrolyte, preparation method thereof and lithium battery |
Non-Patent Citations (1)
| Title |
|---|
| XIAONA LI ET AL.: "Water-Mediated Synthesis of a Superionic Halide Solid Electrolyte", ANGEW. CHEM., vol. 58, no. 46, pages 16427 - 16432 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116799294A (en) * | 2023-08-16 | 2023-09-22 | 有研(广东)新材料技术研究院 | Inorganic solid electrolyte material with high fluorine content and preparation and application thereof |
| CN116799294B (en) * | 2023-08-16 | 2024-02-02 | 有研(广东)新材料技术研究院 | Inorganic solid electrolyte material with high fluorine content and preparation and application thereof |
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