CN110323490A - A kind of Width funtion window inorganic solid electrolyte material and preparation method thereof - Google Patents
A kind of Width funtion window inorganic solid electrolyte material and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
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Abstract
A kind of Width funtion window inorganic solid electrolyte material and preparation method thereof.The chemical formula of solid electrolyte material are as follows: (100-z) (xLi2S·yP2S5) zM, x:y=78:22 (molar ratio) M is lithium halide in formula.The present invention is in 78Li2S·22P2S5Halogenation lithium compound is doped on the basis of material, increase lithium ion transport channel, promote the generation of high conductivity thio-LISICONII object phase, improve lithium ion conductivity, the lithium halide being simultaneously added mutually forms solid solution with high conductivity object, electrolyte electrochemical window has been widened, has enhanced the stability to lithium metal, electrochemical stability is good when matching high-voltage anode material uses.The present invention uses simple mechanical ball mill technology, by being further heat-treated to obtain solid electrolyte material, the electrolyte safety is good, the advantages of having both wide electrochemical window and high ionic conductivity, preparation method is simple, low production cost can be widely applied in solid lithium battery, be expected to realize heavy industrialization application.
Description
Technical field
The invention belongs to new energy fields, are specifically related to field of lithium, more particularly relate to all solid state lithium ion
The preparation method of battery, sulfide solid electrolyte material.
Background technique
Lithium ion secondary battery is occupied an important position in new energy field, due to comparing function with operating voltage height
Rate is high, and specific energy is big, good cycle, and memory-less effect and environmental-friendly feature are widely used in mobile phone, pen
Remember in the equipment such as this computer, digital camera, wearable intelligent electric appliance.In recent years, with electronics miniaturization, integrated, electricity
The rise of electrical automobile industry and extensive energy-accumulating power station, thus structure to lithium ion battery and performance propose it is more harsh
Requirement.
Currently, widely used lithium ion battery, under the high temperature conditions can oxygen using liquid electrolyte on the market
Change and decompose, generate gas, leakage etc., these unstable factors bring great security risk to the use of lithium ion battery.
Meanwhile for highly integrated small-sized electronic product and wearable intelligent equipment, the lithium ion battery of conventional liquid electrolyte is simultaneously
It is impossible to meet the demands of application, and the all-solid lithium-ion battery of solid electrolyte is used to have as the energy storage device of a new generation
Have broad application prospects, relative to traditional liquid electrolyte, solid electrolyte has preferable thermal stability, electrochemistry steady
Qualitative and excellent machining property is expected to fundamentally solve the safety issue of battery, also can satisfy lithium battery in spy
Use under the conditions of different, based on the advantage in safety and energy density, solid electrolyte substitution conventional liquid electrolyte is considered
The only way of the following lithium battery development, in lithium battery energy storage battery field, all-solid lithium-ion battery is electric car and scale
Change the ideal electrochmical power source of energy storage.
Solid electrolyte is broadly divided into organic polymer species electrolyte, inorganic oxide species electrolyte and inorganic sulphide species
Electrolyte.Typical Representative of the sulfide electrolyte as inorganic solid electrolyte has ionic conductivity height, electrochemical window mouth width
With excellent mechanical performance, so as to cause extensive concern.Instantly, by Japanese Scientists Noriaki Kamaya invention
Li10GeP2S12Electrolyte, the electrolyte are body-centered cubic structure, have three-dimensional lithium ion transport channel, and voltage window reaches 5V,
Ionic conductivity has reached the level of liquid electrolyte under room temperature.Get a good chance of being applied in solid lithium battery, so
And Li10GeP2S12Starting material GeS2Expensive, which greatly limits the industrial applications of such material.Therefore, it develops
A kind of low in cost, ionic conductivity height has both the inorganic solid electrolyte material of voltage window mouth width, to high-energy density, Gao An
The application of full solid lithium battery has great importance.
Summary of the invention
The purpose of the present invention is to provide a kind of Width funtion window inorganic solid electrolyte material and preparation method thereof, the electricity
The advantages of solution material preparation method for material is simple, low in cost, has both ionic conductivity height and electrochemical window mouth width can match high electricity
Cobalt acid lithium is pressed, nickel-cobalt-manganternary ternary anode material improves energy density, power density, operating temperature range and the safety of battery
Property.Solid foundation has been established for the industrial applications of all-solid-state battery.
A kind of Width funtion window inorganic solid electrolyte material, it is characterised in that the chemical formula of solid electrolyte material
Are as follows:
(100-z)(xLi2S·yP2S5) zM (1),
Wherein x:y=78:22；M is lithium halide, 0≤z≤30.
Further, lithium halide LiF, LiCl, LiBr and LiI are one such or a variety of.
The preparation method of Width funtion window inorganic solid electrolyte material as described above, which is characterized in that preparation process packet
Include following steps:
A. under the protection of inert atmosphere, by Li2S, P2S5, lithium halide three is mixed according to the proportion as shown in chemical formula (1)
It closes, is packed into ball grinder and carries out mechanical ball mill, prepare electrolyte precursor non-crystalline material；
B. the presoma amorphous material prepared is heat-treated under vacuum condition or inert atmosphere, is obtained such as formula
(1) Width funtion window inorganic solid electrolyte material shown in.
Further, the mechanical ball mill used is high-energy ball milling；High-energy ball milling revolving speed is set as 180-600rpm, when ball milling
Between be set as 5-70h, wherein every ball milling 30-50min, ball mill stops interval 10min；Ball material mass ratio is set as (5~80):
1。
Further, the inert atmosphere is argon gas or nitrogen atmosphere.
Further, heat treatment includes the temperature-rise period in two stages, in which:
The first stage heat treatment temperature is 120~190 DEG C, and the setting time is 0.2~4 hour；The second stage
Heat treatment temperature is 210~360 DEG C, and the setting time is 1~6 hour.
The present invention is with Li2S、P2S5, lithium halide be raw material, preparation process mainly include mechanical ball mill prepare presoma powder,
Heat treatment obtains final material, obtains the Width funtion window inorganic solid electrolyte material as shown in formula (1).The present invention is original
Halogenation lithium compound is introduced on the basis of binary electrolyte material, halogen ion has been integrated into whole solid-solution structures well and has worked as
In, the defect that halogen ion is oxidized is compensated for, electrolyte electrochemical window has been widened.The presence of halogen ion improves sulfide
Stability between electrolyte and lithium metal, meanwhile, the doping of lithium halide provides multidimensional lithium ion transport channel, enhances lithium
Ions mobile space, improves lithium ion conductivity.
The invention has the benefit that
1, electrolyte prepared by the present invention is raw materials used cheap, and heat treatment temperature is low, and preparation process is simple, easily operated,
This is highly beneficial to the following large-scale industrial production.
2, the present invention prepared by Width funtion window inorganic solid electrolyte material under the premise of guaranteeing high ionic conductivity,
With wide electrochemical window, high-voltage anode material use can be matched, and lithium metal is stablized, can be applied to all solid state
In lithium ion battery, the safety and energy density of lithium ion battery are greatly improved.
Detailed description of the invention
Fig. 1 is the electrochemical window of Width funtion window inorganic solid electrolyte material prepared by present example 1,
Fig. 2 is the Arrhenius curve of Width funtion window inorganic solid electrolyte prepared by present example 1.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, in conjunction with the following drawings and embodiment, right
The present invention is described in further detail.Described herein the specific embodiments are only for explaining the present invention, is not used to limit
The present invention.
The present invention cover any substitution made on the essence and scope of the present invention being defined by the claims, modification, etc.
Efficacious prescriptions method and scheme.It is detailed below in datail description of the invention in order to make the public have a better understanding the present invention
Describe some specific detail sections.The present invention provides a kind of Width funtion window inorganic solid electrolyte material and preparation sides
Method, protection scope of the present invention are not limited by the following examples.
Example 1: under an argon atmosphere, by analytically pure Li2S、P2S5After being weighed according to molar ratio 78:22, according still further to
(78Li2S·22P2S5): LiI is added in the molar ratio of LiI=90:10, oxygen content and water content≤condition of 0.1ppm
Under with the revolving speed ball milling of 520rpm, ratio of grinding media to material is set as 30:1, and Ball-milling Time is set as 25h, obtains powder after ball milling
Material is sealed into quartz ampoule, is heat-treated under an argon atmosphere, then 170 DEG C of heat preservation 0.5h, 260 DEG C of heat preservation 2h are cooled to the furnace
Room temperature.The sample after heat treatment is taken out under the conditions of water content≤0.1ppm, the powder ground is Width funtion window
Inorganic solid electrolyte material, i.e. 90% (78Li2S·22P2S5) 10%LiI (mol%) glass ceramics.
By 90% (78Li obtained above2S·22P2S5) 10%LiI (mol%) glass ceramics pressed by powder is at diameter
For the thin slice of 10mm, AC impedance is tested using stainless steel substrates as blocking electrode in both sides on electrochemical workstation, and setting frequency is joined
Number is 0.1-1MHz, and sweeping speed is 5mv/s, then calculates its conductivity.As the result is shown: under conditions of 25 DEG C, lithium-ion electric
Conductance is 5.2 × 10-3Scm-1, with cyclic voltammetry electrolyte electrochemical window, method particularly includes: be with stainless steel substrates
Working electrode, lithium piece is for reference electrode and to electrode, and sweeping speed is 0.5mv/s, and potential region is -0.5-6V.
Example 2: under an argon atmosphere, by analytically pure Li2S、P2S5After being weighed according to molar ratio 78:22, according still further to
(78Li2S·22P2S5): LiI is added in the molar ratio of LiI=80:20, oxygen content and water content≤condition of 0.1ppm
Under mixed with the revolving speed ball milling of 300rpm, ratio of grinding media to material is set as 40:1, and Ball-milling Time is set as 20h, obtains powder after ball milling
Shape material is sealed into quartz ampoule, is heat-treated under an argon atmosphere, 160 DEG C of heat preservation 0.5h, 270 DEG C of heat preservation 2h, then cold with furnace
But to room temperature.The sample after heat treatment is taken out under the conditions of water content≤0.1ppm, the powder ground is Width funtion
Window inorganic solid electrolyte material, i.e. 80% (78Li2S·22P2S5) 20%LiI (mol%) glass ceramics.
By 80% (78Li obtained above2S·22P2S5) 20%LiI (mol%) glass ceramics pressed by powder is at diameter
For the thin slice of 10mm, AC impedance is tested using stainless steel substrates as blocking electrode in both sides on electrochemical workstation, and setting frequency is joined
Number is 0.1-1MHz, and sweeping speed is 5mv/s, then calculates its conductivity.As the result is shown: under conditions of 25 DEG C, lithium-ion electric
Conductance is 3.7 × 10-3Scm-1, with cyclic voltammetry electrolyte electrochemical window, method particularly includes: be with stainless steel substrates
Working electrode, lithium piece is for reference electrode and to electrode, and sweeping speed is 0.5mv/s, and potential region is -0.5-6V.
Example 3: under an argon atmosphere, by analytically pure Li2S、P2S5After being weighed according to molar ratio 78:22, according still further to
(78Li2S·22P2S5): LiI is added in the molar ratio of LiI=70:30, oxygen content and water content≤condition of 0.1ppm
Under with the revolving speed ball milling of 400rpm, ratio of grinding media to material is set as 45:1, and Ball-milling Time is set as 15h, obtains powder after ball milling
Material is sealed into quartz ampoule, is heat-treated under an argon atmosphere, then 170 DEG C of heat preservation 0.5h, 280 DEG C of heat preservation 2h are cooled to the furnace
Room temperature.The sample after heat treatment is taken out under the conditions of water content≤0.1ppm, the powder ground is Width funtion window
Inorganic solid electrolyte material, i.e. 70% (78Li2S·22P2S5) 30%LiI (mol%) glass ceramics.
By 70% (78Li obtained above2S·22P2S5) 30%LiI (mol%) glass ceramics pressed by powder is at diameter
For the thin slice of 10mm, AC impedance is tested using stainless steel substrates as blocking electrode in both sides on electrochemical workstation, and setting frequency is joined
Number is 0.1-1MHz, and sweeping speed is 5mv/s, then calculates its conductivity.As the result is shown: under conditions of 25 DEG C, lithium-ion electric
Conductance is 2.6 × 10-3Scm-1, with cyclic voltammetry electrolyte electrochemical window, method particularly includes: be with stainless steel substrates
Working electrode, lithium piece is for reference electrode and to electrode, and sweeping speed is 0.5mv/s, and potential region is -0.5-6V.
Example 4: under an argon atmosphere, by analytically pure Li2S、P2S5After being weighed according to molar ratio 78:22, according still further to
(78Li2S·22P2S5): LiBr is added in the molar ratio of LiBr=95:5, oxygen content and water content≤condition of 0.1ppm
Under with the revolving speed ball milling of 520rpm, ratio of grinding media to material is set as 30:1, and Ball-milling Time is set as 25h, obtains powder after ball milling
Material is sealed into quartz ampoule, is heat-treated under an argon atmosphere, then 180 DEG C of heat preservation 0.5h, 270 DEG C of heat preservation 2h are cooled to the furnace
Room temperature.The sample after heat treatment is taken out under the conditions of water content≤0.1ppm, the powder ground is Width funtion window
Inorganic solid electrolyte material.That is 95% (78Li2S·22P2S5) 5%LiBr (mol%) glass ceramics.
By 95% (78Li obtained above2S·22P2S5) 5%LiBr (mol%) glass ceramics pressed by powder is at diameter
For the thin slice of 10mm, AC impedance is tested using stainless steel substrates as blocking electrode in both sides on electrochemical workstation, and setting frequency is joined
Number is 0.1-1MHz, and sweeping speed is 5mv/s, then calculates its conductivity.As the result is shown: under conditions of 25 DEG C, lithium-ion electric
Conductance is 4.2 × 10-3Scm-1, with cyclic voltammetry electrolyte electrochemical window, method particularly includes: be with stainless steel substrates
Working electrode, lithium piece is for reference electrode and to electrode, and sweeping speed is 0.5mv/s, and potential region is -0.5-6V.
Example 5: under an argon atmosphere, by analytically pure Li2S、P2S5After being weighed according to molar ratio 78:22, according still further to
(78Li2S·22P2S5): LiBr is added in the molar ratio of LiBr=85:15, oxygen content and water content≤item of 0.1ppm
With the revolving speed ball milling of 300rpm under part, ratio of grinding media to material is set as 40:1, and Ball-milling Time is set as 20h, obtains powdery after ball milling
Material is sealed into quartz ampoule, is heat-treated under an argon atmosphere, 190 DEG C of heat preservation 0.5h, 300 DEG C of heat preservation 2h, then furnace cooling
To room temperature.The sample after heat treatment is taken out under the conditions of water content≤0.1ppm, the powder ground is Width funtion window
Mouth inorganic solid electrolyte material, i.e. 85% (78Li2S·22P2S5) 15%LiBr (mol%) glass ceramics.
By 85% (78Li obtained above2S·22P2S5) 15%LiBr (mol%) glass ceramics pressed by powder Cheng Zhi
Diameter is the thin slice of 10mm, and both sides test AC impedance using stainless steel substrates as blocking electrode on electrochemical workstation, frequency is arranged
Parameter is 0.1-1MHz, and sweeping speed is 5mv/s, then calculates its conductivity.As the result is shown: under conditions of 25 DEG C, lithium ion
Conductivity is 3.7 × 10-3Scm-1, with cyclic voltammetry electrolyte electrochemical window, method particularly includes: with stainless steel substrates
For working electrode, lithium piece is for reference electrode and to electrode.Sweeping speed is 0.5mv/s, and potential region is -0.5-6V.
Example 6: under an argon atmosphere, by analytically pure Li2S、P2S5After being weighed according to molar ratio 78:22, according still further to
(78Li2S·22P2S5): LiBr is added in the molar ratio of LiBr=75:25, oxygen content and water content≤item of 0.1ppm
With the revolving speed ball milling of 600rpm under part, ratio of grinding media to material is set as 45:1, and Ball-milling Time is set as 15h, obtains powdery after ball milling
Material is sealed into quartz ampoule, is heat-treated under an argon atmosphere, 170 DEG C of heat preservation 0.5h, 290 DEG C of heat preservation 2h, then furnace cooling
To room temperature.The sample after heat treatment is taken out under the conditions of water content≤0.1ppm, the powder ground is Width funtion window
Mouth inorganic solid electrolyte material, i.e. 75% (78Li2S·22P2S5) 25%LiBr (mol%) glass ceramics.
By 75% (78Li obtained above2S·22P2S5) 25%LiBr (mol%) glass ceramics pressed by powder Cheng Zhi
Diameter is the thin slice of 10mm, and both sides test AC impedance using stainless steel substrates as blocking electrode on electrochemical workstation, frequency is arranged
Parameter is 0.1-1MHz, and sweeping speed is 5mv/s, then calculates its conductivity.As the result is shown: under conditions of 25 DEG C, lithium ion
Conductivity is 2.1 × 10-3Scm-1, with cyclic voltammetry electrolyte electrochemical window, method particularly includes: with stainless steel substrates
For working electrode, lithium piece is for reference electrode and to electrode, and sweeping speed is 0.5mv/s, and potential region is -0.5-6V.
Example 7: under an argon atmosphere, by analytically pure Li2S、P2S5After being weighed according to molar ratio 78:22, according still further to
(78Li2S·22P2S5): LiCl is added in the molar ratio of LiCl=99:1, oxygen content and water content≤condition of 0.1ppm
Under mixed with the revolving speed ball milling of 300rpm, ratio of grinding media to material is set as 30:1, and Ball-milling Time is set as 25h, obtains powder after ball milling
Shape material is sealed into quartz ampoule, is heat-treated under an argon atmosphere, 160 DEG C of heat preservation 0.5h, 280 DEG C of heat preservation 2h, then cold with furnace
But to room temperature.The sample after heat treatment is taken out under the conditions of water content≤0.1ppm, the powder ground is Width funtion
Window inorganic solid electrolyte material.That is 99% (78Li2S·22P2S5) 1%LiCl (mol%) glass ceramics.
By 99% (78Li obtained above2S·22P2S5) 1%LiCl (mol%) glass ceramics pressed by powder is at diameter
For the thin slice of 10mm, AC impedance is tested using stainless steel substrates as blocking electrode in both sides on electrochemical workstation, and setting frequency is joined
Number is 0.1-1MHz, and sweeping speed is 5mv/s, then calculates its conductivity.As the result is shown: under conditions of 25 DEG C, lithium-ion electric
Conductance is 2.3 × 10-3Scm-1, with cyclic voltammetry electrolyte electrochemical window, method particularly includes: be with stainless steel substrates
Working electrode, lithium piece is for reference electrode and to electrode, and sweeping speed is 0.5mv/s, and potential region is -0.5-6V.
Example 8: under an argon atmosphere, by analytically pure Li2S、P2S5After being weighed according to molar ratio 78:22, according still further to
(78Li2S·22P2S5): LiCl is added in the molar ratio of LiCl=89:11, oxygen content and water content≤item of 0.1ppm
With the revolving speed ball milling of 500rpm under part, ratio of grinding media to material is set as 40:1, and Ball-milling Time is set as 20h, obtains powdery after ball milling
Material is sealed into quartz ampoule, is heat-treated under an argon atmosphere, 180 DEG C of heat preservation 0.5h, 300 DEG C of heat preservation 2h, then furnace cooling
To room temperature.The sample after heat treatment is taken out under the conditions of water content≤0.1ppm, the powder ground is Width funtion window
Mouth inorganic solid electrolyte material, i.e. 89% (78Li2S·22P2S5) 11%LiCl (mol%) glass ceramics.
By 89% (78Li obtained above2S·22P2S5) 11%LiCl (mol%) glass ceramics pressed by powder Cheng Zhi
Diameter is the thin slice of 10mm, and both sides test AC impedance using stainless steel substrates as blocking electrode on electrochemical workstation, frequency is arranged
Parameter is 0.1-1MHz, and sweeping speed is 5mv/s, then calculates its conductivity.As the result is shown: under conditions of 25 DEG C, lithium ion
Conductivity is 4.6 × 10-3Scm-1, with cyclic voltammetry electrolyte electrochemical window, method particularly includes: with stainless steel substrates
For working electrode, lithium piece is for reference electrode and to electrode, and sweeping speed is 0.5mv/s, and potential region is -0.5-6V.
Example 9: under an argon atmosphere, by analytically pure Li2S、P2S5After being weighed according to molar ratio 78:22, according still further to
(78Li2S·22P2S5): LiCl is added in the molar ratio of LiCl=79:21, oxygen content and water content≤item of 0.1ppm
With the revolving speed ball milling of 550rpm under part, ratio of grinding media to material is set as 45:1, and Ball-milling Time is set as 15h, obtains powdery after ball milling
Material is sealed into quartz ampoule, is heat-treated under an argon atmosphere, 190 DEG C of heat preservation 0.5h, 320 DEG C of heat preservation 2h, then furnace cooling
To room temperature.The sample after heat treatment is taken out under the conditions of water content≤0.1ppm, the powder ground is Width funtion window
Mouth inorganic solid electrolyte material, i.e. 79% (78Li2S·22P2S5) 21%LiCl (mol%) glass ceramics.
By 79% (78Li obtained above2S·22P2S5) 21%LiCl (mol%) glass ceramics pressed by powder Cheng Zhi
Diameter is the thin slice of 10mm, and both sides test AC impedance using stainless steel substrates as blocking electrode on electrochemical workstation, frequency is arranged
Parameter is 0.1-1MHz, and sweeping speed is 5mv/s, then calculates its conductivity.As the result is shown: under conditions of 25 DEG C, lithium ion
Conductivity is 2.2 × 10-3Scm-1, with cyclic voltammetry electrolyte electrochemical window, method particularly includes: with stainless steel substrates
For working electrode, lithium piece is for reference electrode and to electrode, and sweeping speed is 0.5mv/s, and potential region is -0.5-6V.
Example 10: under an argon atmosphere, by analytically pure Li2S、P2S5After being weighed according to molar ratio 78:22, according still further to
(78Li2S·22P2S5): LiF is added in the molar ratio of LiF=90:10, oxygen content and water content≤condition of 0.1ppm
Under with the revolving speed ball milling of 520rpm, ratio of grinding media to material is set as 30:1, and Ball-milling Time is set as 25h, obtains powder after ball milling
Material is sealed into quartz ampoule, is heat-treated under an argon atmosphere, then 160 DEG C of heat preservation 0.5h, 270 DEG C of heat preservation 2h are cooled to the furnace
Room temperature.The sample after heat treatment is taken out under the conditions of water content≤0.1ppm, the powder ground is Width funtion window
Inorganic solid electrolyte material.That is 90% (78Li2S·22P2S5) 10%LiF (mol%) glass ceramics.
By 90% (78Li obtained above2S·22P2S5) 10%LiF (mol%) glass ceramics pressed by powder is at diameter
For the thin slice of 10mm, AC impedance is tested using stainless steel substrates as blocking electrode in both sides on electrochemical workstation, and setting frequency is joined
Number is 0.1-1MHz, and sweeping speed is 5mv/s, then calculates its conductivity.As the result is shown: under conditions of 25 DEG C, lithium-ion electric
Conductance is 2.4 × 10-3Scm-1, with cyclic voltammetry electrolyte electrochemical window, method particularly includes: be with stainless steel substrates
Working electrode, lithium piece is for reference electrode and to electrode, and sweeping speed is 0.5mv/s, and potential region is -0.5-6V.
Example 11: under an argon atmosphere, by analytically pure Li2S、P2S5After being weighed according to molar ratio 78:22, according still further to
(78Li2S·22P2S5): LiF is added in the molar ratio of LiF=80:20, oxygen content and water content≤condition of 0.1ppm
Under with the revolving speed ball milling of 550rpm, ratio of grinding media to material is set as 40:1, and Ball-milling Time is set as 20h, obtains powder after ball milling
Material is sealed into quartz ampoule, is heat-treated under an argon atmosphere, 180 DEG C of heat preservation 0.5h, 280 DEG C of heat preservation 2h, then cold with furnace
But to room temperature.The sample after heat treatment is taken out under the conditions of water content≤0.1ppm, the powder ground is Width funtion
Window inorganic solid electrolyte material, i.e. 80% (78Li2S·22P2S5) 20%LiF (mol%) glass ceramics.
By 80% (78Li obtained above2S·22P2S5) 20%LiF (mol%) glass ceramics pressed by powder is at diameter
For the thin slice of 10mm, AC impedance is tested using stainless steel substrates as blocking electrode in both sides on electrochemical workstation, and setting frequency is joined
Number is 0.1-1MHz, and sweeping speed is 5mv/s, then calculates its conductivity.As the result is shown: under conditions of 25 DEG C, lithium-ion electric
Conductance is 1.9 × 10-3Scm-1, with cyclic voltammetry electrolyte electrochemical window, method particularly includes: be with stainless steel substrates
Working electrode, lithium piece is for reference electrode and to electrode, and sweeping speed is 0.5mv/s, and potential region is -0.5-6V.
Example 12: under an argon atmosphere, by analytically pure Li2S、P2S5After being weighed according to molar ratio 78:22, according still further to
(78Li2S·22P2S5): LiF is added in the molar ratio of LiF=70:30, oxygen content and water content≤condition of 0.1ppm
Under with the revolving speed ball milling of 600rpm, ratio of grinding media to material is set as 45:1, and Ball-milling Time is set as 15h, obtains powder after ball milling
Material is sealed into quartz ampoule, is heat-treated under an argon atmosphere, 180 DEG C of heat preservation 0.5h, 310 DEG C of heat preservation 2h, then cold with furnace
But to room temperature.The sample after heat treatment is taken out under the conditions of water content≤0.1ppm, the powder ground is Width funtion
Window inorganic solid electrolyte material, i.e. 70% (78Li2S·22P2S5) 30%LiF (mol%) glass ceramics.
By 70% (78Li obtained above2S·22P2S5) 30%LiF (mol%) glass ceramics pressed by powder is at diameter
For the thin slice of 10mm, AC impedance is tested using stainless steel substrates as blocking electrode in both sides on electrochemical workstation, and setting frequency is joined
Number is 0.1-1MHz, and sweeping speed is 5mv/s, then calculates its conductivity.As the result is shown: under conditions of 25 DEG C, lithium-ion electric
Conductance is 1.3 × 10-3Scm-1, with cyclic voltammetry electrolyte electrochemical window, method particularly includes: be with stainless steel substrates
Working electrode, lithium piece is for reference electrode and to electrode, and sweeping speed is 0.5mv/s, and potential region is -0.5-6V.
Claims (6)
1. a kind of Width funtion window inorganic solid electrolyte material, it is characterised in that the chemical formula of solid electrolyte material are as follows:
(100-z)(xLi2S·yP2S5) zM (1),
Wherein x:y=78:22；M is lithium halide, 0≤z≤30.
2. Width funtion window inorganic solid electrolyte material according to claim 1, which is characterized in that lithium halide LiF,
LiCl, LiBr and LiI are one such or a variety of.
3. the preparation method of Width funtion window inorganic solid electrolyte material as described in claim 1, which is characterized in that prepared
Journey the following steps are included:
A. under the protection of inert atmosphere, by Li2S, P2S5, lithium halide three according to as shown in chemical formula (1) match mix,
It is packed into ball grinder and carries out mechanical ball mill, prepare electrolyte precursor non-crystalline material；
B. the presoma amorphous material prepared is heat-treated under vacuum condition or inert atmosphere, is obtained such as formula (1) institute
The Width funtion window inorganic solid electrolyte material shown.
4. the preparation method of Width funtion window inorganic solid electrolyte material as claimed in claim 3, which is characterized in that use
Mechanical ball mill is high-energy ball milling；High-energy ball milling revolving speed is set as 180-600rpm, and Ball-milling Time is set as 5-70h, wherein every ball
30-50min is ground, ball mill stops interval 10min；Ball material mass ratio is set as (5~80): 1.
5. the preparation method of Width funtion window inorganic solid electrolyte material as claimed in claim 3, which is characterized in that described
Inert atmosphere is argon gas or nitrogen atmosphere.
6. the preparation method of Width funtion window inorganic solid electrolyte material as claimed in claim 3, which is characterized in that heat treatment
Temperature-rise period including two stages, in which:
The first stage heat treatment temperature is 120~190 DEG C, and the setting time is 0.2~4 hour；At the second stage heat
Managing temperature is 210~360 DEG C, and the setting time is 1~6 hour.
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| CN102891299A (en) * | 2012-09-12 | 2013-01-23 | 黎军 | High-rate lithium ion battery cathode material and preparation method and application thereof |
| CN105140560A (en) * | 2015-09-15 | 2015-12-09 | 中国科学院宁波材料技术与工程研究所 | Lithium ion solid conductor stable on metal lithium, preparation method of lithium ion solid conductor, and full-solid lithium secondary battery |
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| CN102891299A (en) * | 2012-09-12 | 2013-01-23 | 黎军 | High-rate lithium ion battery cathode material and preparation method and application thereof |
| CN105140560A (en) * | 2015-09-15 | 2015-12-09 | 中国科学院宁波材料技术与工程研究所 | Lithium ion solid conductor stable on metal lithium, preparation method of lithium ion solid conductor, and full-solid lithium secondary battery |
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| CN111740152A (en) * | 2020-07-22 | 2020-10-02 | 多氟多新能源科技有限公司 | High-performance sulfide solid electrolyte and preparation method thereof |
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