CN105140560B - Stable lithium ion solid conductor of a kind of pair of lithium metal and preparation method thereof and a kind of all solid lithium secondary battery - Google Patents
Stable lithium ion solid conductor of a kind of pair of lithium metal and preparation method thereof and a kind of all solid lithium secondary battery Download PDFInfo
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- CN105140560B CN105140560B CN201510585679.XA CN201510585679A CN105140560B CN 105140560 B CN105140560 B CN 105140560B CN 201510585679 A CN201510585679 A CN 201510585679A CN 105140560 B CN105140560 B CN 105140560B
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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
- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
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Abstract
The present invention provides one kind lithium ion solid conductor material as shown in formula (I), (100-x) (yLi2S·zP2S5) xM, in formula (I): 0 < x≤40, y:z=3:1；M is lithium halide.Lithium ion solid conductor of the invention is due to introducing halogenation lithium compound into sulfide electrolyte, so that effect forms a buffer layer between halogen atom and lithium metal, such as the SEI film in liquid lithium battery, electrolyte ingredient is effectively relieved to react with the further of lithium metal, improves the stability of electrolyte and metal lithium electrode.In addition, introducing halogenation lithium compound into sulfide electrolyte provides the more-dimensional channels of lithium ion transport, its activity space is increased, the raising of lithium ion conductivity is resulted in.Therefore, the introducing of lithium halide can also be improved the ionic conductivity of sulfide electrolyte.
Description
Technical field
The invention belongs to technical field of lithium batteries, and in particular to the stable lithium ion solid conductor material of a kind of pair of lithium metal
And preparation method thereof and a kind of all solid lithium secondary battery.
Background technique
All solid lithium secondary battery refers to that battery each unit includes anode, cathode and electrolyte, all using solid-state material
The lithium secondary battery of material.Lithium secondary battery with output power, energy density is high, cyclicity is superior, memory-less effect with it is acyclic
The many advantages such as border pollution are widely applied in daily life, and the first choice for becoming the rechargable power supplies of portable electronic product is right
As being also considered as most competitive Vehicular dynamic battery.Since all solid lithium secondary battery has liquid lithium secondary battery
Incomparable safety, and be expected to thoroughly eliminate the security risk in use process, more meet electric car and scale energy storage
The demand of field future development.
Currently, the lithium ion battery using graphite as cathode is widely used to each electronic product, however the reason of graphite
There was only 372mAh/g by specific capacity, and there are larger irreversible capacity losses during first charge-discharge, so being difficult to become height
The negative electrode material of specific energy secondary cell.
With the continuous development of science and technology and the urgent need to high-energy-density negative electrode material, lithium metal is as secondary cell
The research of negative electrode material paid close attention to again.Lithium metal relative standard's hydrogen electrode potential is -3.045V, and specific capacity is
3861mAh/g is ideal high-energy lithium cell cathode material.Its charge density is very big and has stable helium type
Electric double layer so that it is easy to polarize other molecules or ion, therefore has very big unstability.Basically,
Lithium metal is used as secondary battery negative pole, and main problem is: (1) lower charge and discharge caused by complicated interfacial reaction
Cycle efficieny and interface impedance are continuously increased；(2) generation of " dendrite " and " dead lithium ", brought safety issue and electrode
Active material loss.Both of these problems seriously constrain current lithium base secondary cell, including lithium ion battery, all solid lithium electricity
The development in pond, lithium-sulfur cell and lithium-air battery becomes its major technology bottleneck.
The next-generation lithium battery with high energy storage of exploitation, needs lithium metal as the electrolyte of cathode and high voltage.
And current electrolysis material mostly uses greatly sulfide solid electrolyte, sulfide solid electrolyte is due to relatively high electricity
Conductance and wide electrochemical window are a kind of inoganic solids lithium ion conductors that can be advantageously applied to all solid lithium secondary battery
Material.However, sulfide solid electrolyte significantly limits it in all solid lithium secondary battery to the unstability of lithium metal
In development and application.
Therefore, develop to lithium metal chemical stabilization and with the new material of good lithium ion conducting characteristic, it is all kinds of to developing
High-energy density, macrocyclic solid state secondary battery technology based on lithium anode are of great significance.
Summary of the invention
In view of this, being led the technical problem to be solved in the present invention is that providing a kind of pair of stable lithium ion solid of lithium metal
Body material and preparation method thereof and a kind of all solid lithium secondary battery, lithium ion solid conductor material provided by the invention is to gold
Belong to lithium to stablize, and there is good chemical property.
The present invention provides one kind lithium ion solid conductor material as shown in formula (I),
(100-x)(yLi2S·zP2S5) xM formula (I)
In formula (I): 0 < x≤40, y:z=3:1；
M is lithium halide.
Preferably, 0 < x≤20.
Preferably, 0.5 < x≤16.
Preferably, M LiF, LiCl, LiBr or LiI.
The present invention also provides the preparation method of one kind lithium ion solid conductor material as shown in formula (I), including it is following
Step:
A) by Li2S、P2S5With M mixed grinding, initial material is obtained；
B) under conditions of inert gas, the initial material is heat-treated, obtains the lithium ion solid as shown in formula (I)
Conductor material；
(100-x)(yLi2S·zP2S5) xM formula (I)
In formula (I): 0 < x≤40, y:z=3:1；
M is lithium halide.
Preferably, described to be ground to mechanical lapping.
Preferably, the mechanical lapping is high-energy ball milling, and the revolving speed of the high-energy ball milling is 200~500rpm, and the time is
5h~60h, ratio of grinding media to material are (1~60): 1.
Preferably, the inert gas is selected from nitrogen or argon gas.
Preferably, the temperature of the heat treatment is 100~500 DEG C, and the time is 0.5~20h.
The present invention also provides a kind of all solid lithium secondary battery, including anode, cathode and electrolyte, the electrolyte
The lithium ion solid conductor material being prepared for above-mentioned lithium ion solid conductor material or above-mentioned preparation method.
Compared with prior art, the present invention provides one kind lithium ion solid conductor material, (100- as shown in formula (I)
x)(yLi2S·zP2S5) xM, in formula (I): 0 < x≤40, y:z=3:1；M is lithium halide.Lithium ion solid conductor of the invention
Due to introducing halogenation lithium compound into sulfide electrolyte, so that effect formation one is slow between halogen atom and lithium metal
Layer is rushed, such as the SEI film in liquid lithium battery, electrolyte ingredient is effectively relieved and is reacted with the further of lithium metal, is improved
The stability of electrolyte and metal lithium electrode.In addition, introducing halide into sulfide electrolyte provides lithium ion transport
More-dimensional channels increase its activity space, result in the raising of lithium ion conductivity.Therefore, the introducing of lithium halide can also mention
The ionic conductivity of high-sulfur compound electrolyte.
The result shows that electricity lithium ion solid conductor material prepared by the present invention between lithium metal with not having in 6000 minutes
Have and apparent electrochemical reaction occurs, it is with good stability.Its optimal conductivity is 1.13 × 10-3~1.93 × 10-3S
cm-1, as the temperature rises, conductivity is also correspondingly improved.The electric lithium ion solid conductor material assembling preparation is helped
Solid state battery recycles 100 weeks there is no obviously decaying, and the optimal capacity retention ratio of battery reaches 90.3%~93.4%.
Detailed description of the invention
Fig. 1 is the AC impedance spectroscopy of lithium ion solid conductor material prepared by the embodiment of the present invention 1；
Fig. 2 is the conductivity map under lithium ion solid conductor material different temperatures prepared by the embodiment of the present invention 1；
Fig. 3 is the lithium ion solid conductor material of the preparation of the embodiment of the present invention 1 to lithium stability test result；
Fig. 4 is that the cycle performance for the battery that lithium ion solid conductor material prepared by the embodiment of the present invention 1 is prepared is surveyed
Attempt；
Fig. 5 is the lithium ion solid conductor material of the preparation of the embodiment of the present invention 5 to lithium stability test result；
Fig. 6 is that the cycle performance for the battery that lithium ion solid conductor material prepared by the embodiment of the present invention 5 is prepared is surveyed
Attempt；
Fig. 7 is the lithium ion solid conductor material of the preparation of the embodiment of the present invention 8 to lithium stability test result；
Fig. 8 is that the cycle performance for the battery that lithium ion solid conductor material prepared by the embodiment of the present invention 8 is prepared is surveyed
Attempt；
Fig. 9 is the lithium ion solid conductor material of the preparation of the embodiment of the present invention 11 to lithium stability test result；
Figure 10 is the cycle performance for the battery that lithium ion solid conductor material prepared by the embodiment of the present invention 11 is prepared
Test chart；
Figure 11 is the conductivity of lithium ion solid conductor material prepared by the embodiment of the present invention 1~12.
Specific embodiment
The present invention provides one kind lithium ion solid conductor material as shown in formula (I),
(100-x)(yLi2S·zP2S5) xM formula (I)
In formula (I): 0 < x≤40, y:z=3:1；
M is lithium halide.
Lithium ion solid conductor material provided by the invention is that halogenation lithium compound is introduced into sulfide, in the present invention
In, the sulfide has the atomic ratio of formula (II),
yLi2S·zP2S5Formula (II)
Wherein, in formula (II), the molar ratio of the y and z are 3:1.
The halogenation lithium compound is M, it is preferred that the M is selected from LiF, LiCl, LiBr or LiI.
In lithium ion solid conductor material provided by the invention, the molar ratio of sulfide and M shown in the formula (II)
Preferably (100-x): x.Wherein, 0 < x≤40, it is preferred that 0 < x≤20, it is furthermore preferred that 0.5 < x≤16.
The present invention also provides the preparation method of one kind lithium ion solid conductor material as shown in formula (I), including it is following
Step:
A) by Li2S、P2S5With M mixed grinding, initial material is obtained；
B) under conditions of inert gas, the initial material is heat-treated, obtains the lithium ion solid as shown in formula (I)
Conductor material；
(100-x)(yLi2S·zP2S5) xM formula (I)
In formula (I): 0 < x≤40, y:z=3:1；
M is lithium halide.
The present invention is first by Li2S、P2S5With M mixed grinding, initial material is obtained.In the present invention, it is preferred in inert gas
Under the conditions of carry out Li2S、P2S5Weighing and mixed grinding with M, the inert gas are preferably nitrogen or argon gas.Wherein, institute
State Li2S and P2S5Molar ratio be preferably 3:1, Li2S and P2S5The molar ratio of the sulfide and M that are mixed to get is preferably (100-
X): x.Wherein, 0 < x≤40, it is preferred that 0 < x≤20, it is furthermore preferred that 0.5 < x≤16.
The present invention is to the Li2S、P2S5There is no specifically limited, those skilled in the art's public affairs with the mode of M mixed grinding
The method for the mixed grinding known.In the present invention, it is preferred to using mechanical lapping, more preferably high-energy ball milling.The high energy
The revolving speed of ball milling is 200~500rpm, preferably 300~400rpm；The time of the high-energy ball milling is 5h~60h, preferably
10~30h；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, lithium ion solid conductor material can be obtained.
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 the tabletting
Method there is no specifically limited, well known to a person skilled in the art tabletting methods.In the present invention, it is preferred to according to as follows
Method carries out tabletting:
Initial material after the grinding is subjected to tabletting under the pressure condition of 10MPa, 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, is obtained
To the lithium ion solid conductor material as shown in formula (I).In the present invention, the inert gas is preferably nitrogen or argon gas.Institute
The temperature for stating heat treatment is 100~500 DEG C, preferably 200~500 DEG C；The time of the heat treatment is 0.5~20h, preferably
1~10h.
The specific method of heat treatment of the present invention is preferably as follows:
The sheet initial material is heated with the heating rate of 1~3 DEG C/min, is warming up to 100~500 DEG C, heat preservation 0.5~
It cools to room temperature after 20h with the furnace, obtains sheet lithium ion solid conductor material.
The present invention also provides a kind of all solid lithium secondary battery, including anode, cathode and electrolyte, the electrolyte
The lithium ion solid conductor material being prepared for above-mentioned lithium ion solid conductor material or above-mentioned preparation method.In the present invention
In, the anode is preferably cobalt acid lithium, LiMn2O4, LiFePO4, more preferably cobalt acid lithium；The cathode is preferably Carbon anode,
Lithium anode, more preferably lithium anode material.
Lithium ion solid conductor of the invention is due to introducing halogenation lithium compound into sulfide electrolyte, so that halogen
Effect forms a buffer layer and electrolyte is effectively relieved such as the SEI film in liquid lithium battery between atom and lithium metal
Ingredient is reacted with the further of lithium metal, improves the stability of electrolyte and metal lithium electrode.In addition, into sulfide electrolyte
It introduces halide and provides the more-dimensional channels of lithium ion transport, increase its activity space, result in mentioning for lithium ion conductivity
It is high.Therefore, the introducing of lithium halide can also be improved the ionic conductivity of sulfide electrolyte.
The result shows that electricity lithium ion solid conductor material prepared by the present invention between lithium metal with not having in 6000 minutes
Have and apparent electrochemical reaction occurs, it is with good stability.Its optimal conductivity is 1.13 × 10-3~1.93 × 10-3S
cm-1, as the temperature rises, conductivity is also correspondingly improved.The electric lithium ion solid conductor material assembling preparation is helped
Solid state battery recycles 100 weeks there is no obviously decaying, and the optimal capacity retention ratio of battery reaches 90.3%~93.4%.
For a further understanding of the present invention, below with reference to embodiment to lithium ion solid conductor material provided by the invention and
Preparation method and a kind of all solid lithium secondary battery are illustrated, and protection scope of the present invention is not by the limit of following embodiment
System.
Embodiment 1
It is respectively 99% or more Li by purity under argon atmosphere protection2S、P2S5After being weighed according to molar ratio 75:25,
(75Li is pressed again2S·25P2S5): LiI is added in the molar ratio of LiI=90:10, under conditions of water content is less than 10ppm with
500rpm revolving speed ground and mixed uniformly, powder initial material is obtained under the conditions of 45:1 ratio of grinding media to material after high-energy ball milling 12h, take out powder initial material
It is finely ground that sheet initial material is uniformly obtained using the tabletting of 10MPa pressure afterwards, sheet initial material is packed into sintering mold.Above-mentioned sheet will be housed
The sintering mold of initial material is heated to 250 DEG C with the heating rate of 2 DEG C/min, keeps the temperature 2h, cools to the furnace after room temperature in water content
Less than the grinding of sheet sintered product is taken out under conditions of 100ppm uniformly, it is solid for all solid lithium secondary battery lithium ion to obtain powder
Body conductor material, i.e. 90% (75Li2S·25P2S5) 10%LiI (mol%) glass ceramics.
To 90% (75Li2S·25P2S5) 10%LiI (mol%) lithium ion solid conductor material progress chemical property
It tests and to lithium stability test.Above-mentioned lithium ion solid conductor powder body material is less than 10ppm, 10MPa pressure in water content
Under the conditions of, being pressed into diameter is 10mm, the 90% (75Li of sheet with a thickness of 1mm2S·25P2S5) 10%LiI (mol%) glass
Glass ceramics lithium ion solid conductor.Then using carbon as blocking electrode, EIS test is carried out at different temperatures, tests its electric conductivity
Can, the AC impedance spectroscopy of the lithium ion solid conductor material as a result prepared as shown in FIG. 1, FIG. 1 is the embodiment of the present invention 1, Fig. 2
It is the conductivity under its different temperatures.It will be seen from figure 1 that this system has ionic conduction characteristic, and under the conditions of 25 DEG C,
Lithium ion conductivity is 1.61 × 10-3S cm-1, show that resulting all solid lithium secondary battery lithium ion solid conductor material exists
There is good electric conductivity at room temperature, Fig. 2 shows the conduction for being conducive to material to lithium ion with the raising of operating temperature.
90% (the 75Li that will be obtained2S·25P2S5) 10%LiI (mol%) lithium ion solid conductor, it is clipped in two gold
Belong to lithium in electrode, it is carried out to lithium stability test, test results are shown in figure 3.Itself the result shows that, in 6000 minutes,
Electrolyte is prepared with, there is no apparent electrochemical reaction, totality is with good stability between lithium metal.
It uses cobalt acid lithium for anode, uses lithium metal for cathode, be assembled into together with above-mentioned lithium ion solid conductor material
All solid lithium secondary battery, first charge-discharge curve graph see Fig. 4.From fig. 4, it can be seen that all-solid-state battery recycles 100 weeks
There is no significantly decaying, battery still has extraordinary capacity, and capacity retention ratio reaches 93.4%.
Embodiment 2
It is respectively 99% or more Li by purity under argon atmosphere protection2S、P2S5After being weighed according to molar ratio 75:25,
Pressing (75Li2S·25P2S5): LiI is added in the molar ratio of LiI=95:5, under conditions of water content is less than 10ppm with
200rpm revolving speed ground and mixed uniformly, powder initial material is obtained under the conditions of 40:1 ratio of grinding media to material after high-energy ball milling 18h, take out powder initial material
It is finely ground that sheet initial material is uniformly obtained using the tabletting of 10MPa pressure afterwards, sheet initial material is packed into sintering mold.Above-mentioned sheet will be housed
The sintering mold of initial material is heated to 300 DEG C with the heating rate of 1 DEG C/min, keeps the temperature 4h, cools to the furnace after room temperature in water content
Less than the grinding of sheet sintered product is taken out under conditions of 100ppm uniformly, powder all solid lithium secondary battery lithium ion solid is obtained
Conductor material, i.e. 95% (75Li2S·25P2S5) 5%LiI (mol%) glass ceramics.
Test the present embodiment obtains the electrification of all solid lithium secondary battery lithium ion solid conductor according to the method for embodiment 1
Learn performance characterization.The results show that lithium ion conductivity is 8.1 × 10 under the conditions of 25 DEG C-4S cm-1, test result is as schemed
Shown in 11.
Embodiment 3
It is respectively 99% or more Li by purity under argon atmosphere protection2S、P2S5After being weighed according to molar ratio 75:25,
Pressing (75Li2S·25P2S5): LiI is added in the molar ratio of LiI=85:15, under conditions of water content is less than 10ppm with
300rpm revolving speed ground and mixed uniformly, powder initial material is obtained under the conditions of 30:1 ratio of grinding media to material after high-energy ball milling 22h, take out powder initial material
It is finely ground that sheet initial material is uniformly obtained using the tabletting of 10MPa pressure afterwards, sheet initial material is packed into sintering mold.Above-mentioned sheet will be housed
The sintering mold of initial material is heated to 350 DEG C with the heating rate of 2 DEG C/min, keeps the temperature 8h, cools to the furnace after room temperature in water content
Less than the grinding of sheet sintered product is taken out under conditions of 100ppm uniformly, powder all solid lithium secondary battery lithium ion solid is obtained
Conductor material, i.e. 85% (75Li2S·25P2S5) 15%LiI (mol%) glass ceramics.
Test the present embodiment obtains the electrification of all solid lithium secondary battery lithium ion solid conductor according to the method for embodiment 1
Learn performance characterization.The results show that lithium ion conductivity is 6.2 × 10 under the conditions of 25 DEG C-4S cm-1, test result is as schemed
Shown in 11.
Embodiment 4
It is respectively 99% or more Li by purity under argon atmosphere protection2S、P2S5After being weighed according to molar ratio 75:25,
Pressing (75Li2S·25P2S5): LiBr is added in the molar ratio of LiBr=99:1, under conditions of water content is less than 10ppm with
200rpm revolving speed ground and mixed uniformly, powder initial material is obtained under the conditions of 30:1 ratio of grinding media to material after high-energy ball milling 28h, take out powder initial material
It is finely ground that sheet initial material is uniformly obtained using the tabletting of 10MPa pressure afterwards, sheet initial material is packed into sintering mold.Above-mentioned sheet will be housed
The sintering mold of initial material is heated to 200 DEG C with the heating rate of 1 DEG C/min, keeps the temperature 10h, cools to the furnace after room temperature in water content
Less than the grinding of sheet sintered product is taken out under conditions of 100ppm uniformly, powder all solid lithium secondary battery lithium ion solid is obtained
Conductor material, i.e. 99% (75Li2S·25P2S5) 1%LiBr (mol%) glass ceramics.
Test the present embodiment obtains the electrification of all solid lithium secondary battery lithium ion solid conductor according to the method for embodiment 1
Learn performance characterization.The results show that lithium ion conductivity is 6 × 10 under the conditions of 25 DEG C-4S cm-1, test result such as Figure 11
It is shown.
Embodiment 5
It is respectively 99% or more Li by purity under argon atmosphere protection2S、P2S5After being weighed according to molar ratio 75:25,
Pressing (75Li2S·25P2S5): LiBr is added in the molar ratio of LiBr=95:5, under conditions of water content is less than 10ppm with
500rpm revolving speed ground and mixed uniformly, powder initial material is obtained under the conditions of 45:1 ratio of grinding media to material after high-energy ball milling 12h, take out powder initial material
It is finely ground that sheet initial material is uniformly obtained using the tabletting of 10MPa pressure afterwards, sheet initial material is packed into sintering mold.Above-mentioned sheet will be housed
The sintering mold of initial material is heated to 250 DEG C with the heating rate of 2 DEG C/min, keeps the temperature 2h, cools to the furnace after room temperature in water content
Less than the grinding of sheet sintered product is taken out under conditions of 100ppm uniformly, powder all solid lithium secondary battery lithium ion solid is obtained
Conductor material, i.e. 95% (75Li2S·25P2S5) 5%LiBr (mol%) glass ceramics.
Test the present embodiment obtains the electrification of all solid lithium secondary battery lithium ion solid conductor according to the method for embodiment 1
Learn performance characterization.The results show that lithium ion conductivity is 1.93 × 10 under the conditions of 25 DEG C-3S cm-1, test result is as schemed
Shown in 11.It is carried out to lithium stability test by 1 method of embodiment, test results are shown in figure 5.In 6000 minutes, preparation
Electrolyte between lithium metal with, there is no apparent electrochemical reaction, having good stability.All solid lithium two is assembled by example 1
Primary cell, first charge-discharge curve graph see Fig. 6.All-solid-state battery recycle 100 weeks there is no obviously decaying, battery capacity
Conservation rate reaches 91.3%.
Embodiment 6
It is respectively 99% or more Li by purity under argon atmosphere protection2S、P2S5After being weighed according to molar ratio 75:25,
Pressing (75Li2S·25P2S5): LiBr is added in the molar ratio of LiBr=90:10, under conditions of water content is less than 10ppm with
300rpm revolving speed ground and mixed uniformly, powder initial material is obtained under the conditions of 55:1 ratio of grinding media to material after high-energy ball milling 10h, take out powder initial material
It is finely ground that sheet initial material is uniformly obtained using the tabletting of 10MPa pressure afterwards, sheet initial material is packed into sintering mold.Above-mentioned sheet will be housed
The sintering mold of initial material is heated to 450 DEG C with the heating rate of 2 DEG C/min, keeps the temperature 3h, cools to the furnace after room temperature in water content
Less than the grinding of sheet sintered product is taken out under conditions of 100ppm uniformly, powder all solid lithium secondary battery lithium ion solid is obtained
Conductor material, i.e. 90% (75Li2S·25P2S5) 10%LiBr (mol%) glass ceramics.
Test the present embodiment obtains the electrification of all solid lithium secondary battery lithium ion solid conductor according to the method for embodiment 1
Learn performance and structural characterization.The results show that lithium ion conductivity is 2 × 10 under the conditions of 25 DEG C-4S cm-1, test result
As shown in figure 11.
Embodiment 7
It is respectively 99% or more Li by purity under argon atmosphere protection2S、P2S5After being weighed according to molar ratio 75:25,
Pressing (75Li2S·25P2S5): LiCl is added in the molar ratio of LiCl=99:1, under conditions of water content is less than 10ppm with
300rpm revolving speed ground and mixed uniformly, powder initial material is obtained under the conditions of 30:1 ratio of grinding media to material after high-energy ball milling 26h, take out powder initial material
It is finely ground that sheet initial material is uniformly obtained using the tabletting of 10MPa pressure afterwards, sheet initial material is packed into sintering mold.Above-mentioned sheet will be housed
The sintering mold of initial material is heated to 200 DEG C with the heating rate of 2 DEG C/min, keeps the temperature 3h, cools to the furnace after room temperature in water content
Less than the grinding of sheet sintered product is taken out under conditions of 100ppm uniformly, powder all solid lithium secondary battery lithium ion solid is obtained
Conductor material, i.e. 99% (75Li2S·25P2S5) 1%LiCl (mol%) glass ceramics.
Test the present embodiment obtains the electrification of all solid lithium secondary battery lithium ion solid conductor according to the method for embodiment 1
Learn performance characterization.The results show that lithium ion conductivity is 7 × 10 under the conditions of 25 DEG C-4S cm-1, test result such as Figure 11
It is shown.
Embodiment 8
It is respectively 99% or more Li by purity under argon atmosphere protection2S、P2S5After being weighed according to molar ratio 75:25,
Pressing (75Li2S·25P2S5): LiCl is added in the molar ratio of LiCl=95:5, under conditions of water content is less than 10ppm with
500rpm revolving speed ground and mixed uniformly, powder initial material is obtained under the conditions of 45:1 ratio of grinding media to material after high-energy ball milling 12h, take out powder initial material
It is finely ground that sheet initial material is uniformly obtained using the tabletting of 10MPa pressure afterwards, sheet initial material is packed into sintering mold.Above-mentioned sheet will be housed
The sintering mold of initial material is heated to 250 DEG C with the heating rate of 2 DEG C/min, keeps the temperature 2h, cools to the furnace after room temperature in water content
Less than the grinding of sheet sintered product is taken out under conditions of 100ppm uniformly, powder all solid lithium secondary battery lithium ion solid is obtained
Conductor material, i.e. 95% (75Li2S·25P2S5) 5%LiCl (mol%) glass ceramics.
Test the present embodiment obtains the electrification of all solid lithium secondary battery lithium ion solid conductor according to the method for embodiment 1
Learn performance and structural characterization.The results show that lithium ion conductivity is 1.27 × 10 under the conditions of 25 DEG C-3S cm-1, test knot
Fruit is as shown in figure 11.It is carried out to lithium stability test by 1 method of embodiment, test results are shown in figure 7.6000 minutes
It is interior, electrolyte is prepared with, there is no apparent electrochemical reaction, having good stability between lithium metal.It is assembled into entirely by example 1
Solid lithium secondary cell, first charge-discharge curve graph see Fig. 8.All-solid-state battery recycle 100 weeks there is no obviously decaying,
Battery capacity conservation rate reaches 92.3%.
Embodiment 9
It is respectively 99% or more Li by purity under argon atmosphere protection2S、P2S5After being weighed according to molar ratio 75:25,
Pressing (75Li2S·25P2S5): LiCl is added in the molar ratio of LiCl=90:10, under conditions of water content is less than 10ppm with
400rpm revolving speed ground and mixed uniformly, powder initial material is obtained under the conditions of 55:1 ratio of grinding media to material after high-energy ball milling 10h, take out powder initial material
It is finely ground that sheet initial material is uniformly obtained using the tabletting of 10MPa pressure afterwards, sheet initial material is packed into sintering mold.Above-mentioned sheet will be housed
The sintering mold of initial material is heated to 450 DEG C with the heating rate of 3 DEG C/min, keeps the temperature 6h, cools to the furnace after room temperature in water content
Less than the grinding of sheet sintered product is taken out under conditions of 100ppm uniformly, powder all solid lithium secondary battery lithium ion solid is obtained
Conductor material, i.e. 90% (75Li2S·25P2S5) 10%LiCl (mol%) glass ceramics.
Test the present embodiment obtains the electrification of all solid lithium secondary battery lithium ion solid conductor according to the method for embodiment 1
Learn performance characterization.The results show that lithium ion conductivity is 3.1 × 10 under the conditions of 25 DEG C-4S cm-1, test result is as schemed
Shown in 11.
Embodiment 10
It is respectively 99% or more Li by purity under argon atmosphere protection2S、P2S5After being weighed according to molar ratio 75:25,
Pressing (75Li2S·25P2S5): LiF is added in the molar ratio of LiF=99:1, under conditions of water content is less than 10ppm with
400rpm revolving speed ground and mixed uniformly, powder initial material is obtained under the conditions of 55:1 ratio of grinding media to material after high-energy ball milling 10h, take out powder initial material
It is finely ground that sheet initial material is uniformly obtained using the tabletting of 10MPa pressure afterwards, sheet initial material is packed into sintering mold.Above-mentioned sheet will be housed
The sintering mold of initial material is heated to 200 DEG C with the heating rate of 1 DEG C/min, keeps the temperature 1h, cools to the furnace after room temperature in water content
Less than the grinding of sheet sintered product is taken out under conditions of 100ppm uniformly, powder all solid lithium secondary battery lithium ion solid is obtained
Conductor material, i.e. 99% (75Li2S·25P2S5) 1%LiF (mol%) glass ceramics.
Test the present embodiment obtains the electrification of all solid lithium secondary battery lithium ion solid conductor according to the method for embodiment 1
Learn performance characterization.The results show that lithium ion conductivity is 7.1 × 10 under the conditions of 25 DEG C-4S cm-1, test result is as schemed
Shown in 11.
Embodiment 11
It is respectively 99% or more Li by purity under argon atmosphere protection2S、P2S5After being weighed according to molar ratio 75:25,
Pressing (75Li2S·25P2S5): LiF is added in the molar ratio of LiF=95:5, under conditions of water content is less than 10ppm with
500rpm revolving speed ground and mixed uniformly, powder initial material is obtained under the conditions of 45:1 ratio of grinding media to material after high-energy ball milling 12h, take out powder initial material
It is finely ground that sheet initial material is uniformly obtained using the tabletting of 10MPa pressure afterwards, sheet initial material is packed into sintering mold.Above-mentioned sheet will be housed
The sintering mold of initial material is heated to 250 DEG C with the heating rate of 2 DEG C/min, keeps the temperature 2h, cools to the furnace after room temperature in water content
Less than the grinding of sheet sintered product is taken out under conditions of 100ppm uniformly, powder all solid lithium secondary battery lithium ion solid is obtained
Conductor material, i.e. 95% (75Li2S·25P2S5) 5%LiF (mol%) glass ceramics.
Test the present embodiment obtains the electrification of all solid lithium secondary battery lithium ion solid conductor according to the method for embodiment 1
Learn performance and structural characterization.The results show that lithium ion conductivity is 1.13 × 10 under the conditions of 25 DEG C-3S cm-1, test knot
Fruit is as shown in figure 11.It is carried out to lithium stability test by 1 method of embodiment, test results are shown in figure 9.6000 minutes
It is interior, electrolyte is prepared with, there is no apparent electrochemical reaction, having good stability between lithium metal.It is assembled into entirely by example 1
Solid lithium secondary cell, first charge-discharge curve graph see Figure 10, and there is no obviously declining in 100 weeks for all-solid-state battery circulation
Subtract, battery capacity conservation rate reaches 90.3%.
Embodiment 12
It is respectively 99% or more Li by purity under argon atmosphere protection2S、P2S5After being weighed according to molar ratio 75:25,
Pressing (75Li2S·25P2S5): LiF is added in the molar ratio of LiF=90:10, under conditions of water content is less than 10ppm with
300rpm revolving speed ground and mixed uniformly, powder initial material is obtained under the conditions of 35:1 ratio of grinding media to material after high-energy ball milling 22h, take out powder initial material
It is finely ground that sheet initial material is uniformly obtained using the tabletting of 10MPa pressure afterwards, sheet initial material is packed into sintering mold.Above-mentioned sheet will be housed
The sintering mold of initial material is heated to 450 DEG C with the heating rate of 3 DEG C/min, keeps the temperature 6h, cools to the furnace after room temperature in water content
Less than the grinding of sheet sintered product is taken out under conditions of 100ppm uniformly, powder all solid lithium secondary battery lithium ion solid is obtained
Conductor material, i.e. 90% (75Li2S·25P2S5) 10%LiF (mol%) glass ceramics.
Test the present embodiment obtains the electrification of all solid lithium secondary battery lithium ion solid conductor according to the method for embodiment 1
Learn performance characterization.The results show that lithium ion conductivity is 6.1 × 10 under the conditions of 25 DEG C-4S cm-1, test result is as schemed
Shown in 11.
The above is only a 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 are also answered
It is considered as protection scope of the present invention.
Claims (7)
1. a kind of lithium ion solid conductor material stable to lithium metal as shown in formula (I),
(100-x)(75Li2S·25P2S5) xM formula (I)
In formula (I): x=5, M LiF, LiCl or LiBr；
X=10, M LiI.
2. a kind of preparation method of lithium ion solid conductor material stable to lithium metal as shown in formula (I), which is characterized in that
The following steps are included:
A) by Li2S、P2S5With M mixed grinding, initial material is obtained；
B) under conditions of inert gas, the initial material is heat-treated, obtains the lithium ion solid conductor as shown in formula (I)
Material；
(100-x)(75Li2S·25P2S5) xM formula (I)
In formula (I): x=5, M LiF, LiCl or LiBr；
X=10, M LiI.
3. preparation method according to claim 2, which is characterized in that described to be ground to mechanical lapping.
4. preparation method according to claim 3, which is characterized in that the mechanical lapping is high-energy ball milling, the high energy
The revolving speed of ball milling is 200~500rpm, and the time is 5h~60h, and ratio of grinding media to material is (1~60): 1.
5. preparation method according to claim 2, which is characterized in that the inert gas is selected from argon gas.
6. preparation method according to claim 2, which is characterized in that the temperature of the heat treatment is 100~500 DEG C, when
Between be 0.5~20h.
7. a kind of all solid lithium secondary battery, which is characterized in that including anode, cathode and electrolyte, the electrolyte is power
Benefit require 1 described in the lithium that is prepared of lithium ion solid conductor material or the described in any item preparation methods of claim 2~6
Ion solid conductor material.
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| CN106169607A (en) * | 2016-08-10 | 2016-11-30 | 中国科学院西安光学精密机械研究所 | One mixes oxygen-lithium ion solid electrolyte and preparation method thereof |
| CN106684432B (en) * | 2017-01-25 | 2019-02-05 | 浙江大学 | High ionic conductivity sulfide solid electrolyte material and its preparation method and application |
| CN107069080A (en) * | 2017-02-13 | 2017-08-18 | 桂林电器科学研究院有限公司 | A kind of lithium sulfide system solid electrolyte material for adding lithium-tin alloy and silver chlorate and preparation method thereof |
| US10903478B2 (en) * | 2018-04-06 | 2021-01-26 | GM Global Technology Operations LLC | Protective coating for lithium-containing electrode and methods of making the same |
| CN108899580A (en) * | 2018-07-02 | 2018-11-27 | 中国科学院宁波材料技术与工程研究所 | A kind of lithium ion solid conductor, preparation method and solid lithium battery |
| CN109638360B (en) * | 2018-11-09 | 2022-03-08 | 哈尔滨工业大学无锡新材料研究院 | Preparation method and preparation mold of all-solid-state lithium-sulfur battery |
| KR20200107396A (en) * | 2019-03-07 | 2020-09-16 | 삼성전자주식회사 | Sulfide-based solid electrolyte, Solid state secondary battery comprising sulfide-based solid electrolyte, and Method for preparing sulfide-based solid electrolyte |
| CN109950617B (en) * | 2019-03-20 | 2022-02-15 | 深圳先进技术研究院 | Inorganic chloride-based solid electrolyte and preparation method and application thereof |
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| CN110911733A (en) * | 2019-10-25 | 2020-03-24 | 浙江锋锂新能源科技有限公司 | Lithium-stable sulfide solid electrolyte, preparation method thereof and solid-state battery with solid electrolyte |
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