CN108258303A - A kind of sulfide solid electrolyte, preparation method and all solid lithium secondary battery - Google Patents
A kind of sulfide solid electrolyte, preparation method and all solid lithium secondary battery 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
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Abstract
The present invention provides a kind of sulfide solid electrolyte, with the chemical formula shown in Formulas I or Formula II：Li3+3xP1‑xZnxS4‑xOxFormulas I；Li3P1‑xSbxS4‑2.5xO2.5xFormula II；Wherein, 0.01≤x≤0.05.The application is by by a certain amount of ZnO or Sb2O5To sulfide solid electrolyte material Li3PS4Codope modification is carried out, can not only improve the air stability of modified sulfide solid electrolyte, but also is conducive to improve lithium ion conductivity.Preparation method and a kind of all solid lithium secondary battery the present invention also provides a kind of sulfide solid electrolyte.
Description
Technical field
The invention belongs to lithium battery technology field more particularly to a kind of sulfide solid electrolyte, preparation method and
All solid lithium secondary battery.
Background technology
Energy crisis and environmental pollution had become restrict human social outstanding problem, exploitation and
Seem more and more urgent using green clean energy resource.Electrochemical energy storage technology can be again for the intermittent cleaning such as solar energy, wind energy
The utilization of the raw energy is most important, while is also the core of zero-emission pure electric automobile.Therefore, efficient, safety, capacity are developed
Greatly, service life is long, and can stablize the energy storage device to release energy when in use and be of great significance.Lithium ion battery is because of its energy
The features such as metric density is high, service life is long is considered as one of electrochemical energy storage technology of most competitiveness.
However, existing lithium ion battery due to use inflammable liquid organic electrolyte, there are leakage, burn into burning or even
The security risks such as explosion.At present, with the development of the technologies such as power battery, intelligent grid energy storage, the safety of lithium ion battery
It can require to be further improved.With all solid state of the traditional liquid organic electrolyte of inorganic solid electrolyte substitution of good security
Lithium battery is the effective way for solving lithium ion battery safety problem.In addition to this, it can replace the diaphragm in lithium battery completely,
So as to be further simplified the structure of battery, battery energy density is improved, facilitate its production and is used, breaks through the limit of cell shapes
System, while battery production cost is reduced, there is great application potential.
Compared with other inorganic solid electrolyte materials, the sulfide solid electrolyte room temperature electricity of thio-LISICON structures
Conductance is relatively high, and with wide electrochemical window, can be applied to all solid lithium secondary battery.However, most of sulfide
Solid electrolyte air stability is bad, and deliquescence easily occurs after contacting with the air, generates hydrogen sulfide gas, therefore uses process must
It must carry out in confined conditions, increase preparation and the use cost of battery.In addition, current inorganic sulphide electrolytic conductivity
There is still a need for the needs further improved to meet lithium battery real work, therefore, preparation has the higher li ionic conductivity, air steady
Fixed solid electrolyte is that all solid lithium secondary battery is made to obtain the key point of practical application, improves sulfide solid electrolyte
The air stability of material has practical value, to developing all kinds of high-energy densities, macrocyclic all solid lithium secondary battery skill
Art is of great significance.
Invention content
The purpose of the present invention is to provide a kind of sulfide solid electrolyte, preparation method and the secondary electricity of all solid lithium
Pond, sulfide solid electrolyte conductivity in the present invention is high, air stability is good.
The present invention provides a kind of sulfide solid electrolyte, with the chemical formula shown in Formulas I or Formula II：
Li3+3xP1-xZnxS4-xOxFormulas I；Li3P1-xSbxS4-2.5xO2.5xFormula II；
Wherein, 0.01≤x≤0.05.
Preferably, the x is 0.01,0.02,0.03,0.04 or 0.05.
The present invention provides a kind of preparation method of sulfide solid electrolyte, includes the following steps：
A it is) 3 by molar ratio:1 Li2S and P2S5With metal oxide mixed grinding, initial material is obtained；The metal oxidation
Object is zinc oxide or antimony oxide；
The metal oxide be zinc oxide, Li2S、P2S5Molar ratio with zinc oxide is (3+3x)：(1-x)：x；
The metal oxide be antimony oxide, Li2S、P2S5Molar ratio with antimony oxide is 3 (1-x)：(1-x)：x.
B) under conditions of inert gas, the initial material is heat-treated, obtains the vulcanization as shown in formula (I) or (II)
Object lithium ion solid electrolyte；
Li3+3xP1-xZnxS4-xOxFormulas I；Li3P1-xSbxS4-2.5xO2.5xFormula II；
Wherein, 0.01≤x≤0.05.
Preferably, it is described to be ground to high-energy ball milling；
The rotating speed of the high-energy ball milling is 200~500rpm；
The time of the high-energy ball milling is 9~18 hours.
Preferably, the ratio of grinding media to material of the high-energy ball milling is (1~60)：1.
Preferably, the temperature of the heat treatment is 150~400 DEG C；
The time of the heat treatment is 1~5 hour.
Preferably, the temperature of the heat treatment is realized by heating up；
The rate of the heating is 1~10 DEG C/min.
The present invention provides a kind of all solid lithium secondary battery, including anode, cathode and electrolyte；
The electrolyte is sulfide solid electrolyte described above.
The present invention provides a kind of sulfide solid electrolyte, with the chemical formula shown in Formulas I or Formula II：Li3+3xP1- xZnxS4-xOxFormulas I；Li3P1-xSbxS4-2.5xO2.5xFormula II；Wherein, 0.01≤x≤0.05.The lithium ion solid electrolyte of the present invention
Material into sulfide electrolyte due to introducing MyOz(M=Zn, Sb) so that oxygen element is added in sulfide solid electrolyte,
And oxonium ion is instead of the bridge joint sulphur that easily react with water of part in solid electrolyte, i.e. P-O-P keys group replaces P-S-P keys group, from
And it avoids P-S-P keys group and generation hydrogen sulfide gas is reacted with the water in air, and then improve sulfide solid electrolyte material
The air stability of material.In addition, MyOzThe i.e. P-O-P keys group that the introducing of (M=Zn, Sb) is formed can increase sulfide solid electrolysis
The chain length of the reticular structure of material, makes the content of S-Li keys increase, and Li ions transmit in sulfide solid electrolyte material
Rely primarily on the Li ions in S-Li keys, therefore MyOzThe introducing of (M=Zn, Sb) can also improve sulfide solid electrolyte
Ionic conductivity.The experimental results showed that the sulfide solid electrolyte conductivity in the present invention is more than 10-3S cm-1(25 DEG C),
The solid lithium battery being assembled into recycles 100 weeks that apparent attenuation does not occur, and battery capacity conservation rate reaches 95.3% He
98.4%.
Description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
The embodiment of invention, for those of ordinary skill in the art, without creative efforts, can also basis
The attached drawing of offer obtains other attached drawings.
Fig. 1 is the air stability test of sulfide electrolyte in the embodiment of the present invention 2；
Fig. 2 is the air stability test of sulfide electrolyte in the embodiment of the present invention 7；
Fig. 3 is sulfide electrolyte in the embodiment of the present invention 2 to the stability test of lithium；
Fig. 4 be the embodiment of the present invention 7 in sulfide electrolyte under different current strength to lithium stability test；
Fig. 5 is the conductivity under sulfide electrolyte different temperatures in the embodiment of the present invention 1~5；
Fig. 6 is the conductivity under sulfide electrolyte different temperatures in the embodiment of the present invention 6~10；
Fig. 7 is the first charge-discharge curve of all solid lithium secondary battery in the embodiment of the present invention 2；
Fig. 8 is the first charge-discharge curve of all solid lithium secondary battery in the embodiment of the present invention 7；
Fig. 9 is the X ray diffracting spectrum of sulfide electrolyte in the embodiment of the present invention 1~5 and comparative example；
Figure 10 is the X ray diffracting spectrum of sulfide electrolyte in the embodiment of the present invention 6~10；
Figure 11 is the air stability test of sulfide electrolyte in comparative example of the present invention；
Figure 12 is the conductivity of sulfide electrolyte at different temperatures in comparative example of the present invention.
Specific embodiment
The present invention provides a kind of sulfide solid electrolyte, with the chemical formula shown in Formulas I or Formula II：
Li3+3xP1-xZnxS4-xOxFormulas I；Li3P1-xSbxS4-2.5xO2.5xFormula II；
Wherein, 0.01≤x≤0.05.
The application is by by a certain amount of ZnO or Sb2O5To sulfide solid electrolyte material Li3PS4Codope is carried out to change
Property, the air stability of modified sulfide solid electrolyte can be not only improved, but also be conducive to improve lithium ion conductivity.
In the present invention, 0.02≤x≤0.04, specifically, x is 0.01,0.02,0.03,0.04 or 0.05.
The present invention also provides a kind of preparation methods of sulfide solid electrolyte, include the following steps：
A) by Li2S and P2S5With metal oxide mixed grinding, initial material is obtained；The metal oxide is zinc oxide or oxygen
Change antimony；
B) under conditions of inert gas, the initial material is heat-treated, obtains the vulcanization as shown in formula (I) or (II)
Object lithium ion solid electrolyte；
Li3+3xP1-xZnxS4-xOxFormulas I；Li3P1-xSbxS4-2.5xO2.5xFormula II；
Wherein, 0.01≤x≤0.05.
The present invention preferably carries out the grinding under an inert gas, and the inert gas is preferably nitrogen or argon gas.
In the present invention, due to the chemical valence of Zn and Sb difference, so Li when being doped2S and P2S5Dosage also have difference
Not, specifically,
When the metal oxide is zinc oxide：
Since Zn is+divalent, but the Zn P elements to be replaced are+5 valencys, accordingly, with respect to ZnO doping system, by following public affairs
Formula carries out raw material ratio.
(1-x) Li3PS4+3xLi2S+xZnO→Li3+3xP1-xZnxS4-xOxFormula III；
Wherein Li3PS4Proportioning be：Li2S:P2S5=3:1；
Therefore, it is integrated according to above-mentioned raw materials proportioning, obtains final raw material proportioning as Li2S、P2S5With zinc oxide
Molar ratio is (3+3x)：(1-x)：x.
When the metal oxide is antimony oxide,
It is consistent with the valence state of P since Sb is+5 valencys, accordingly, with respect to the doping system of antimony oxide, according to it is following match into
Row：
Li2S:P2S5=3:1；Li2S and P2S5Total mole number and antimony oxide molar ratio be (1-x)：x.
Wherein, 0.01≤x≤0.05, it is preferred that 0.02≤x≤0.04, it is furthermore preferred that x=0.02.
The present invention is to the Li2S、P2S5With MyOzThere is no specifically limited, abilities for the mode of (M=Zn, Sb) mixed grinding
The method of mixed grinding well known to field technique personnel.In the present invention, it is preferred to using mechanical lapping, more preferably high energy ball
Mill.The rotating speed of the high-energy ball milling is 200~500rpm, preferably 300~500rpm；The time of the high-energy ball milling for 9h~
18h, preferably 12~15h；The ratio of grinding media to material of the high-energy ball milling is preferably (1~60):1, more preferably (40~55):1.
After grinding, initial material is obtained.The initial material is heat-treated, you can obtain lithium ion solid electrolyte material
Material.Before being heat-treated, the invention also includes the initial material is carried out tabletting, sheet initial material is obtained.The present invention is to described
The method of tabletting is there is no specifically limited, and well known to a person skilled in the art tabletting methods.In the present invention, it is preferred to according to
Following method carries out tabletting：
Initial material after the grinding under the pressure condition of 10~30MPa is subjected to tabletting, obtains sheet initial material.
Obtained sheet initial material is placed in sintering mold by the present invention, under conditions of inert gas, is heat-treated, obtained
To the lithium ion solid electrolyte material as shown in formula (I) (II).In the present invention, the inert gas is preferably nitrogen or argon
Gas.The temperature of the heat treatment is 150~400 DEG C, preferably 150~300 DEG C；The time of the heat treatment is 1~5h, preferably
For 2~5h.
The specific method of heat treatment of the present invention is preferably as follows：
The sheet initial material with the heating rate of 1~10 DEG C/min is heated, 150~400 DEG C is warming up to, keeps the temperature 1~5h
After cool to room temperature with the furnace, obtain sheet lithium ion solid electrolyte.
The present invention also provides a kind of all solid lithium secondary batteries, including anode, cathode and electrolyte, the electrolyte
The lithium ion solid electrolyte material being prepared for above-mentioned lithium ion solid electrolyte material or above-mentioned preparation method.In this hair
In bright, the anode is preferably cobalt acid lithium, LiMn2O4, LiFePO4, more preferably cobalt acid lithium；The cathode is preferably that carbon is born
Pole, lithium anode or its composite material, more preferably lithium anode material.
The present invention provides a kind of sulfide solid electrolyte, with the chemical formula shown in Formulas I or Formula II：Li3+3xP1- xZnxS4-xOxFormulas I；Li3P1-xSbxS4-2.5xO2.5xFormula II；Wherein, 0.01≤x≤0.05.The lithium ion solid electrolyte of the present invention
Material into sulfide electrolyte due to introducing MyOz(M=Zn, Sb) so that oxygen element is added in sulfide solid electrolyte,
And oxonium ion is instead of the bridge joint sulphur that easily react with water of part in solid electrolyte, i.e. P-O-P keys group replaces P-S-P keys group, from
And it avoids P-S-P keys group and generation hydrogen sulfide gas is reacted with the water in air, and then improve sulfide solid electrolyte material
The air stability of material.In addition, MyOzThe i.e. P-O-P keys group that the introducing of (M=Zn, Sb) is formed can increase sulfide solid electrolysis
The chain length of the reticular structure of material, makes the content of S-Li keys increase, and Li ions transmit in sulfide solid electrolyte material
Rely primarily on the Li ions in S-Li keys, therefore MyOzThe introducing of (M=Zn, Sb) can also improve sulfide solid electrolyte
Ionic conductivity.The experimental results showed that the sulfide solid electrolyte conductivity in the present invention is more than 10-3S cm-1(25 DEG C),
The solid lithium battery being assembled into recycles 100 weeks that apparent attenuation does not occur, and battery capacity conservation rate reaches 95.3% He
98.4%.
In order to further illustrate the present invention, a kind of sulfide solid provided by the invention is electrolysed with reference to embodiments
Matter, preparation method and all solid lithium secondary battery are described in detail, but cannot be understood as to the scope of the present invention
Restriction.
Embodiment 1
It is respectively more than 99% Li by purity under argon gas atmosphere protection2S、P2S5, ZnO is according to molar ratio Li2S：
P2S5:ZnO=303:99:2 weigh, water content be less than 10ppm under conditions of with 200rpm rotating speeds ground and mixed uniformly, 10:1
Powder initial material is obtained under the conditions of ratio of grinding media to material after high-energy ball milling 9h, it is finely ground uniformly rear using 10MPa pressure tablettings to take out powder initial material
Sheet initial material is obtained, sheet initial material is packed into sintering mold.By the sintering mold equipped with above-mentioned sheet initial material with the liter of 1 DEG C/min
Warm rate is heated to 150 DEG C, keeps the temperature 1h, and sheet burning is taken out under conditions of water content is less than 100ppm after cooling to room temperature with the furnace
It is uniform to tie product grinding, obtains powder as all solid lithium secondary battery lithium ion solid electrolyte material, i.e. Li3+3xP1-xZnxS4- xOx(x=0.01) glass ceramics.
To Li3+3xP1-xZnxS4-xOx(x=0.01) lithium ion solid electrolyte material carries out crystal structure test and electrification
Learn performance test.Above-mentioned lithium ion solid electrolyte powder body material is less than in water content in 10ppm glove boxes and prepares sample, and
X-ray diffraction test is carried out, it is as shown in Figure 9 to obtain Sample crystals structural information.Above-mentioned lithium ion solid electrolyte powder is existed
Water content is less than under 10ppm, 10MPa pressure condition, is pressed into a diameter of 10mm, the sheet Li that thickness is 1mm3+3xP1-xZnxS4- xOx(x=0.01) glass ceramics lithium ion solid electrolyte.Then using carbon as blocking electrode, EIS surveys are carried out at different temperatures
Examination, tests its electric conductivity, and Fig. 5 is (- 40 under lithium ion solid electrolyte material different temperatures prepared by the embodiment of the present invention 1
DEG C~100 DEG C) conductivity, room-temperature conductivity be 8.82 × 10-4S cm-1。
Embodiment 2
It is respectively more than 99% Li by purity under argon gas atmosphere protection2S、P2S5, ZnO is according to molar ratio Li2S：
P2S5:ZnO=306:98:4 weigh, water content be less than 10ppm under conditions of with 500rpm rotating speeds ground and mixed uniformly, 45:1
Powder initial material is obtained under the conditions of ratio of grinding media to material after high-energy ball milling 13.5h, it is finely ground uniformly rear using 10MPa pressure pressures to take out powder initial material
Piece obtains sheet initial material, and sheet initial material is packed into sintering mold.By the sintering mold equipped with above-mentioned sheet initial material with 2 DEG C/min's
Heating rate is heated to 250 DEG C, keeps the temperature 2h, and sheet is taken out under conditions of water content is less than 100ppm after cooling to room temperature with the furnace
Sintered product grinding is uniform, obtains powder as all solid lithium secondary battery lithium ion solid electrolyte material, i.e. Li3+3xP1- xZnxS4-xOx(x=0.02) glass ceramics.
To Li3+3xP1-xZnxS4-xOx(x=0.02) lithium ion solid electrolyte material carries out Crystal Structure and electrification
Learn performance test.Above-mentioned lithium ion solid electrolyte powder body material is less than in water content in 10ppm glove boxes and prepares sample, and
X-ray diffraction test is carried out, it is as shown in Figure 9 to obtain Sample crystals structural information.
By above-mentioned lithium ion solid electrolyte powder body material in the case where water content is less than 10ppm, 10MPa pressure condition, compacting
Into a diameter of 10mm, the sheet Li that thickness is 1mm3+3xP1-xZnxS4-xOx(x=0.02) glass ceramics lithium ion solid electrolyte.
Then using carbon as blocking electrode, EIS tests are carried out at different temperatures, test its electric conductivity, the results are shown in Figure 5, and Fig. 5 is
The conductivity of lithium ion solid electrolyte prepared by the embodiment of the present invention 2 at different temperatures.From fig. 5, it can be seen that this system
With ionic conduction characteristic, and under the conditions of 25 DEG C, lithium ion conductivity is 1.12 × 10-3S cm-1, show the complete of gained
Solid lithium secondary cell lithium ion solid electrolyte material has good electric conductivity at room temperature, and Fig. 5 shows with work temperature
The raising of degree is conducive to conduction of the material to lithium ion.
The Li that will be obtained3+3xP1-xZnxS4-xOx(x=0.02) lithium ion solid electrolyte is exposed to H2S gases are examined
In the closed container of measurement equipment, container atmosphere is air, and monitors H2S gas contents, the results are shown in Figure 1, at 180 minutes
It is interior, H in container2S gas contents are less than 1ppm, show Li3+3xP1-xZnxS4-xOx(x=0.02) lithium ion solid electrolyte material
To air-stable.
The Li that will be obtained3+3xP1-xZnxS4-xOx(x=0.02) lithium ion solid electrolyte is clipped in two lithium metals to electrode
In, it is carried out to lithium stability test, test result is as shown in Figure 3.Itself the result shows that, in 1500 hours, prepare electrolyte
It is overall with good stability with the apparent electrochemical reaction of generation no between lithium metal.
Cobalt acid lithium is used as anode, uses lithium metal as cathode, is assembled together with above-mentioned lithium ion solid electrolyte material
For all solid lithium secondary battery, first charge-discharge curve graph sees Fig. 7.From figure 7 it can be seen that all-solid-state battery recycles 90 weeks
Later that apparent attenuation does not occur, battery still has extraordinary capacity, and capacity retention ratio reaches 98%.
Embodiment 3
It is respectively more than 99% Li by purity under argon gas atmosphere protection2S、P2S5, ZnO is according to molar ratio Li2S：
P2S5:ZnO=309:97:6 weigh, water content be less than 10ppm under conditions of with 240rpm rotating speeds ground and mixed uniformly, 15:1
Powder initial material is obtained under the conditions of ratio of grinding media to material after high-energy ball milling 10.5h, it is finely ground uniformly rear using 10MPa pressure pressures to take out powder initial material
Piece obtains sheet initial material, and sheet initial material is packed into sintering mold.By the sintering mold equipped with above-mentioned sheet initial material with 3 DEG C/min's
Heating rate is heated to 175 DEG C, keeps the temperature 1.5h, and piece is taken out under conditions of water content is less than 100ppm after cooling to room temperature with the furnace
The grinding of shape sintered product is uniform, obtains powder as all solid lithium secondary battery lithium ion solid electrolyte material, i.e. Li3+3xP1- xZnxS4-xOx(x=0.03) glass ceramics.
To Li3+3xP1-xZnxS4-xOx(x=0.03) lithium ion solid electrolyte material carries out crystal structure test and electrification
Learn performance test.Above-mentioned lithium ion solid electrolyte powder body material is less than in water content in 10ppm glove boxes and prepares sample, and
X-ray diffraction test is carried out, it is as shown in Figure 9 to obtain Sample crystals structural information.By above-mentioned lithium ion solid electrolyte powder material
Material is pressed into a diameter of 10mm, the sheet Li that thickness is 1mm in the case where water content is less than 10ppm, 10MPa pressure condition3+3xP1- xZnxS4-xOx(x=0.03) glass ceramics lithium ion solid electrolyte.Then it using carbon as blocking electrode, carries out at different temperatures
EIS is tested, and tests its electric conductivity, and the results are shown in Figure 5, and Fig. 5 is lithium ion solid electrolyte prepared by the embodiment of the present invention 3
Conductivity under material different temperatures, room-temperature conductivity are 1.12 × 10-3S cm-1。
Embodiment 4
It is respectively more than 99% Li by purity under argon gas atmosphere protection2S、P2S5, ZnO is according to molar ratio Li2S：
P2S5:ZnO=312:96:8 weigh, water content be less than 10ppm under conditions of with 200rpm rotating speeds ground and mixed uniformly, 20:1
Powder initial material is obtained under the conditions of ratio of grinding media to material after high-energy ball milling 12h, it is finely ground uniformly rear using 10MPa pressure tablettings to take out powder initial material
Sheet initial material is obtained, sheet initial material is packed into sintering mold.By the sintering mold equipped with above-mentioned sheet initial material with the liter of 4 DEG C/min
Warm rate is heated to 200 DEG C, keeps the temperature 2.5h, and sheet is taken out under conditions of water content is less than 100ppm after cooling to room temperature with the furnace
Sintered product grinding is uniform, obtains powder as all solid lithium secondary battery lithium ion solid electrolyte material, i.e. Li3+3xP1- xZnxS4-xOx(x=0.04) glass ceramics.
To Li3+3xP1-xZnxS4-xOx(x=0.04) lithium ion solid electrolyte material carries out crystal structure test and electrification
Learn performance test.Above-mentioned lithium ion solid electrolyte powder body material is less than in water content in 10ppm glove boxes and prepares sample, and
X-ray diffraction test is carried out, it is as shown in Figure 9 to obtain Sample crystals structural information.By above-mentioned lithium ion solid electrolyte powder material
Material is pressed into a diameter of 10mm, the sheet Li that thickness is 1mm in the case where water content is less than 10ppm, 10MPa pressure condition3+3xP1- xZnxS4-xOx(x=0.04) glass ceramics lithium ion solid electrolyte.Then it using carbon as blocking electrode, carries out at different temperatures
EIS is tested, and tests its electric conductivity, and the results are shown in Figure 5, and Fig. 5 is lithium ion solid electrolyte prepared by the embodiment of the present invention 4
Conductivity under material different temperatures, room-temperature conductivity are 8.41 × 10-4S cm-1。
Embodiment 5
It is respectively more than 99% Li by purity under argon gas atmosphere protection2S、P2S5, ZnO is according to molar ratio Li2S：
P2S5:ZnO=315:95:10 weigh, water content be less than 10ppm under conditions of with 300rpm rotating speeds ground and mixed uniformly, 25:1
Powder initial material is obtained under the conditions of ratio of grinding media to material after high-energy ball milling 16.5h, it is finely ground uniformly rear using 10MPa pressure pressures to take out powder initial material
Piece obtains sheet initial material, and sheet initial material is packed into sintering mold.By the sintering mold equipped with above-mentioned sheet initial material with 5 DEG C/min's
Heating rate is heated to 225 DEG C, keeps the temperature 3h, and sheet is taken out under conditions of water content is less than 100ppm after cooling to room temperature with the furnace
Sintered product grinding is uniform, obtains powder as all solid lithium secondary battery lithium ion solid electrolyte material, i.e. Li3+3xP1- xZnxS4-xOx(x=0.05) glass ceramics.
To Li3+3xP1-xZnxS4-xOx(x=0.05) lithium ion solid electrolyte material carries out crystal structure test and electrification
Learn performance test.Above-mentioned lithium ion solid electrolyte powder body material is less than in water content in 10ppm glove boxes and prepares sample, and
X-ray diffraction test is carried out, it is as shown in Figure 9 to obtain Sample crystals structural information.By above-mentioned lithium ion solid electrolyte powder material
Material is pressed into a diameter of 10mm, the sheet Li that thickness is 1mm in the case where water content is less than 10ppm, 10MPa pressure condition3+3xP1- xZnxS4-xOx(x=0.05) glass ceramics lithium ion solid electrolyte.Then it using carbon as blocking electrode, carries out at different temperatures
EIS is tested, and tests its electric conductivity, and the results are shown in Figure 5, and Fig. 5 is lithium ion solid electrolyte prepared by the embodiment of the present invention 5
Conductivity under material different temperatures, room-temperature conductivity are 5.11 × 10-4S cm-1。
Embodiment 6
It is respectively more than 99% Li by purity under argon gas atmosphere protection2S、P2S5、Sb2O5According to molar ratio Li2S：
P2S5:Sb2O5=75:24:1 weighs, water content be less than 10ppm under conditions of with 340rpm rotating speeds ground and mixed uniformly, 30:1
Powder initial material is obtained under the conditions of ratio of grinding media to material after high-energy ball milling 18h, it is finely ground uniformly rear using 10MPa pressure tablettings to take out powder initial material
Sheet initial material is obtained, sheet initial material is packed into sintering mold.By the sintering mold equipped with above-mentioned sheet initial material with the liter of 6 DEG C/min
Warm rate is heated to 275 DEG C, keeps the temperature 3.5h, and sheet is taken out under conditions of water content is less than 100ppm after cooling to room temperature with the furnace
Sintered product grinding is uniform, obtains powder as all solid lithium secondary battery lithium ion solid electrolyte material, i.e. Li3P1- xSbxS4-2.5xO2.5x(x=0.01) glass ceramics.
To Li3P1-xSbxS4-2.5xO2.5x(x=0.01) lithium ion solid electrolyte material carries out crystal structure test and electricity
Chemical property is tested.Above-mentioned lithium ion solid electrolyte powder body material is less than in water content in 10ppm glove boxes and prepares sample,
And X-ray diffraction test is carried out, it is as shown in Figure 10 to obtain Sample crystals structural information.By above-mentioned lithium ion solid electrolyte powder
Material is pressed into a diameter of 10mm, the sheet Li that thickness is 1mm in the case where water content is less than 10ppm, 10MPa pressure condition3P1- xSbxS4-2.5xO2.5x(x=0.01) glass ceramics lithium ion solid electrolyte.Then using carbon as blocking electrode, at different temperatures
EIS tests are carried out, test its electric conductivity, the results are shown in Figure 6, and Fig. 6 is lithium ion solid electricity prepared by the embodiment of the present invention 6
The conductivity under material different temperatures is solved, room-temperature conductivity is 7.78 × 10-4S cm-1。
Embodiment 7
It is respectively more than 99% Li by purity under argon gas atmosphere protection2S、P2S5、Sb2O5According to molar ratio Li2S：
P2S5:Sb2O5=75:23:2 weigh, water content be less than 10ppm under conditions of with 500rpm rotating speeds ground and mixed uniformly, 45:1
Powder initial material is obtained under the conditions of ratio of grinding media to material after high-energy ball milling 15h, it is finely ground uniformly rear using 10MPa pressure tablettings to take out powder initial material
Sheet initial material is obtained, sheet initial material is packed into sintering mold.By the sintering mold equipped with above-mentioned sheet initial material with the liter of 2 DEG C/min
Warm rate is heated to 250 DEG C, keeps the temperature 2h, and sheet burning is taken out under conditions of water content is less than 100ppm after cooling to room temperature with the furnace
It is uniform to tie product grinding, obtains powder as all solid lithium secondary battery lithium ion solid electrolyte material, i.e. Li3P1-xSbxS4- 2.5xO2.5x(x=0.02) glass ceramics.
To Li3P1-xSbxS4-2.5xO2.5x(x=0.02) lithium ion solid electrolyte material carries out Crystal Structure and electricity
Chemical property is tested.Above-mentioned lithium ion solid electrolyte powder body material is less than in water content in 10ppm glove boxes and prepares sample,
And X-ray diffraction test is carried out, it is as shown in Figure 10 to obtain Sample crystals structural information.
By above-mentioned lithium ion solid electrolyte powder body material in the case where water content is less than 10ppm, 10MPa pressure condition, compacting
Into a diameter of 10mm, the sheet Li that thickness is 1mm3P1-xSbxS4-2.5xO2.5x(x=0.02) glass ceramics lithium ion solid is electrolysed
Matter.Then using lithium metal as symmetry electrode assembled battery Li/ electrolyte/Li, stablizing to lithium under its different current strength is tested
Property, the results are shown in Figure 4.Fig. 4 can be seen that electrolyte Li3P1-xSbxS4-2.5xO2.5x(x=0.02) under different current strength
(1mA cm-2,0.5mA cm-2,0.1mA cm-2) show it is fabulous to lithium stability.Using carbon as blocking electrode, in difference
At a temperature of carry out EIS tests, test its electric conductivity, the results are shown in Figure 6, Fig. 6 be the embodiment of the present invention 7 prepare lithium ion
Conductivity under solid electrolyte material different temperatures.From fig. 6, it can be seen that this system have ionic conduction characteristic, and
Under the conditions of 25 DEG C, lithium ion conductivity is 1.08 × 10-3S cm-1, show gained all solid lithium secondary battery lithium ion solid
Electrolyte at room temperature have good electric conductivity, figure five show the raising with operating temperature be conducive to material to lithium from
The conduction of son.
The Li that will be obtained3P1-xSbxS4-2.5xO2.5x(x=0.02) lithium ion solid electrolyte is exposed to H2S gases
In the closed container of detection device, container atmosphere is air, and monitors H2S gas contents, the results are shown in Figure 2, at 180 minutes
It is interior, H in container2S gas contents are less than 2.5ppm, show Li3P1-xSbxS4-2.5xO2.5x(x=0.02) lithium ion solid electrolyte
Material is to air-stable.
The Li that will be obtained3P1-xSbxS4-2.5xO2.5x(x=0.02) lithium ion solid electrolyte is clipped in two lithium metals to electricity
In extremely, it is carried out to lithium stability test, test result is as shown in Figure 3.Itself the result shows that, in 900 hours, prepare electrolyte
It is overall with good stability with the apparent electrochemical reaction of generation no between lithium metal.
Cobalt acid lithium is used as anode, uses lithium metal as cathode, is assembled together with above-mentioned lithium ion solid electrolyte material
For all solid lithium secondary battery, first charge-discharge curve graph sees Fig. 8.From figure 8, it is seen that all-solid-state battery cycle 100
Week decays that generation is not apparent, and battery still has extraordinary capacity, and capacity retention ratio reaches 98%.
Embodiment 8
It is respectively more than 99% Li by purity under argon gas atmosphere protection2S、P2S5、Sb2O5According to molar ratio Li2S：
P2S5:Sb2O5=75:22:3 weigh, water content be less than 10ppm under conditions of with 360rpm rotating speeds ground and mixed uniformly, 35:1
Powder initial material is obtained under the conditions of ratio of grinding media to material after high-energy ball milling 9h, it is finely ground uniformly rear using 10MPa pressure tablettings to take out powder initial material
Sheet initial material is obtained, sheet initial material is packed into sintering mold.By the sintering mold equipped with above-mentioned sheet initial material with the liter of 7 DEG C/min
Warm rate is heated to 300 DEG C, keeps the temperature 4h, and sheet burning is taken out under conditions of water content is less than 100ppm after cooling to room temperature with the furnace
It is uniform to tie product grinding, obtains powder as all solid lithium secondary battery lithium ion solid electrolyte material, i.e. Li3P1-xSbxS4- 2.5xO2.5x(x=0.03) glass ceramics.
To Li3P1-xSbxS4-2.5xO2.5x(x=0.03) lithium ion solid electrolyte material carries out crystal structure test and electricity
Chemical property is tested.Above-mentioned lithium ion solid electrolyte powder body material is less than in water content in 10ppm glove boxes and prepares sample,
And X-ray diffraction test is carried out, it is as shown in Figure 10 to obtain Sample crystals structural information.By above-mentioned lithium ion solid electrolyte powder
Material is pressed into a diameter of 10mm, the sheet Li that thickness is 1mm in the case where water content is less than 10ppm, 10MPa pressure condition3P1- xSbxS4-2.5xO2.5x(x=0.03) glass ceramics lithium ion solid electrolyte.Then using carbon as blocking electrode, at different temperatures
EIS tests are carried out, test its electric conductivity, as a result as shown in figure 66, Fig. 6 is lithium ion solid prepared by the embodiment of the present invention 8
Conductivity under electrolyte different temperatures, room-temperature conductivity are 7.71 × 10-4S cm-1。
Embodiment 9
It is respectively more than 99% Li by purity under argon gas atmosphere protection2S、P2S5、Sb2O5According to molar ratio Li2S：
P2S5:Sb2O5=75:21:4 weigh, water content be less than 10ppm under conditions of with 400rpm rotating speeds ground and mixed uniformly, 40:1
Powder initial material is obtained under the conditions of ratio of grinding media to material after high-energy ball milling 13.5h, it is finely ground uniformly rear using 10MPa pressure pressures to take out powder initial material
Piece obtains sheet initial material, and sheet initial material is packed into sintering mold.By the sintering mold equipped with above-mentioned sheet initial material with 8 DEG C/min's
Heating rate is heated to 350 DEG C, keeps the temperature 4.5h, and piece is taken out under conditions of water content is less than 100ppm after cooling to room temperature with the furnace
The grinding of shape sintered product is uniform, obtains powder as all solid lithium secondary battery lithium ion solid electrolyte material, i.e. Li3P1- xSbxS4-2.5xO2.5x(x=0.04) glass ceramics.
To Li3P1-xSbxS4-2.5xO2.5x(x=0.04) lithium ion solid electrolyte material carries out crystal structure test and electricity
Chemical property is tested.Above-mentioned lithium ion solid electrolyte powder body material is less than in water content in 10ppm glove boxes and prepares sample,
And X-ray diffraction test is carried out, it is as shown in Figure 10 to obtain Sample crystals structural information.By above-mentioned lithium ion solid electrolyte powder
Material is pressed into a diameter of 10mm, the sheet Li that thickness is 1mm in the case where water content is less than 10ppm, 10MPa pressure condition3P1- xSbxS4-2.5xO2.5x(x=0.04) glass ceramics lithium ion solid electrolyte.Then using carbon as blocking electrode, at different temperatures
EIS tests are carried out, test its electric conductivity, the results are shown in Figure 6, and Fig. 6 is lithium ion solid electricity prepared by the embodiment of the present invention 6
The conductivity under material different temperatures is solved, room-temperature conductivity is 5.84 × 10-4S cm-1。
Embodiment 10
It is respectively more than 99% Li by purity under argon gas atmosphere protection2S、P2S5、Sb2O5According to molar ratio Li2S：
P2S5:Sb2O5=75:20:5 weigh, water content be less than 10ppm under conditions of with 460rpm rotating speeds ground and mixed uniformly, 5:1
Powder initial material is obtained under the conditions of ratio of grinding media to material after high-energy ball milling 10.5h, it is finely ground uniformly rear using 10MPa pressure pressures to take out powder initial material
Piece obtains sheet initial material, and sheet initial material is packed into sintering mold.By the sintering mold equipped with above-mentioned sheet initial material with 10 DEG C/min
Heating rate be heated to 400 DEG C, keep the temperature 5h, piece taken out under conditions of water content is less than 100ppm after cooling to room temperature with the furnace
The grinding of shape sintered product is uniform, obtains powder as all solid lithium secondary battery lithium ion solid electrolyte material, i.e. Li3P1- xSbxS4-2.5xO2.5x(x=0.05) glass ceramics.
To Li3P1-xSbxS4-2.5xO2.5x(x=0.05) lithium ion solid electrolyte material carries out crystal structure test and electricity
Chemical property is tested.Above-mentioned lithium ion solid electrolyte powder body material is less than in water content in 10ppm glove boxes and prepares sample,
And X-ray diffraction test is carried out, it is as shown in Figure 10 to obtain Sample crystals structural information.By above-mentioned lithium ion solid electrolyte powder
Material is pressed into a diameter of 10mm, the sheet Li that thickness is 1mm in the case where water content is less than 10ppm, 10MPa pressure condition3P1- xSbxS4-2.5xO2.5x(x=0.05) glass ceramics lithium ion solid electrolyte.Then using carbon as blocking electrode, at different temperatures
EIS tests are carried out, test its electric conductivity, the results are shown in Figure 6, and Fig. 6 is lithium ion solid electricity prepared by the embodiment of the present invention 6
The conductivity under material different temperatures is solved, room-temperature conductivity is 4.67 × 10-4S cm-1。
Comparative example
It is respectively more than 99% Li by purity under argon gas atmosphere protection2S、P2S5According to molar ratio 75:After 25 weigh,
Water content be less than 10ppm under conditions of with 500rpm rotating speeds ground and mixed uniformly, 45:High-energy ball milling 12h under the conditions of 1 ratio of grinding media to material
Powder initial material is obtained afterwards, and taking-up powder initial material is finely ground uniformly to obtain sheet initial material using 10MPa pressure tablettings afterwards, by sheet initial material
It is packed into sintering mold.Sintering mold equipped with above-mentioned sheet initial material is heated to 270 DEG C with the heating rate of 2 DEG C/min, heat preservation
2h takes out the grinding of sheet sintered product uniformly under conditions of water content is less than 100ppm after cooling to room temperature with the furnace, obtains powder
Body be all solid lithium secondary battery lithium ion solid electrolyte material, i.e. Li3PS4Glass ceramics.
To Li3PS4Lithium ion solid electrolyte material carries out Crystal Structure and electrochemical property test.By above-mentioned lithium
Ion solid electrolyte powder material, which is less than in water content in 10ppm glove boxes, prepares sample, and carry out X-ray diffraction test,
It is as shown in Figure 9 to obtain Sample crystals structural information.
The Li that will be obtained3PS4Lithium ion solid electrolyte is exposed to H2In the closed container of S gas detection equipments,
Container atmosphere is air, and monitors H2S gas contents, as a result as shown in figure 11, in 180 minutes, H in container2S gas contents
Up to 90ppm, show Li3+3xP1-xZnxS4-xOx,Li3P1-xSbxS4-2.5xO2.5x, wherein 0.01≤x≤0.05 lithium ion solid electrolysis
Material is compared to Li3PS4Lithium ion solid electrolyte more stablizes air.Higher lithium ion conductivity is shown simultaneously,
Li3PS4Conductivity under lithium ion solid electrolyte different temperatures is as shown in figure 12, and room-temperature conductivity is 4.1 × 10-4S cm-1。
Above-described embodiment and test result show that in 180 minutes lithium ion solid electrolyte prepared by the present invention is with sky
That apparent chemical reaction, (see Fig. 1, Fig. 2) with good stability does not occur between gas.In 900 hours, present invention system
Standby lithium ion solid conductor material does not have significant reaction with lithium metal, to lithium excellent in stability (see Fig. 3, Fig. 4).Present invention system
Standby lithium ion solid conductor material electric conductivity is more than 10-3S cm-1(25 DEG C), with the raising of temperature, conductivity is also corresponding
It improves (see Fig. 5, Fig. 6).Lithium ion solid conductor material assembling is prepared into solid lithium battery, cycle does not have for 100 weeks
Apparent attenuation occurs, battery capacity conservation rate reaches 95.3% and 98.4% (see Fig. 7, Fig. 8).
The above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of sulfide solid electrolyte, with the chemical formula shown in Formulas I or Formula II：
Li3+3xP1-xZnxS4-xOxFormulas I；Li3P1-xSbxS4-2.5xO2.5xFormula II；
Wherein, 0.01≤x≤0.05.
2. sulfide solid electrolyte according to claim 1, which is characterized in that the x is 0.01,0.02,0.03,
0.04 or 0.05.
3. a kind of preparation method of sulfide solid electrolyte, includes the following steps：
A) by Li2S and P2S5With metal oxide mixed grinding, initial material is obtained；The metal oxide is zinc oxide or oxidation
Antimony；
B) under conditions of inert gas, the initial material is heat-treated, obtains the sulfide lithium as shown in formula (I) or (II)
Ion solid electrolyte；
Li3+3xP1-xZnxS4-xOxFormulas I；Li3P1-xSbxS4-2.5xO2.5xFormula II；
Wherein, 0.01≤x≤0.05.
4. preparation method according to claim 3, which is characterized in that the metal oxide be zinc oxide, Li2S、P2S5
Molar ratio with zinc oxide is (3+3x)：(1-x)：x；
The metal oxide be antimony oxide, Li2S、P2S5Molar ratio with antimony oxide is 3 (1-x)：(1-x)：x.
5. preparation method according to claim 3, which is characterized in that described to be ground to high-energy ball milling；
The rotating speed of the high-energy ball milling is 200~500rpm；
The time of the high-energy ball milling is 9~18 hours.
6. preparation method according to claim 4, which is characterized in that the ratio of grinding media to material of the high-energy ball milling is (1~60)：1.
7. preparation method according to claim 3, which is characterized in that the temperature of the heat treatment is 150~400 DEG C；
The time of the heat treatment is 1~5 hour.
8. preparation method according to claim 6, which is characterized in that the temperature of the heat treatment is realized by heating up；
The rate of the heating is 1~10 DEG C/min.
9. a kind of all solid lithium secondary battery, including anode, cathode and electrolyte；
The electrolyte is arbitrary for the sulfide solid electrolyte described in claim 1~2 any one or claim 3~7
Sulfide solid electrolyte made from preparation method described in one.
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