CN108899526A - A kind of transient metal sulfide electrode material and preparation method thereof and solid lithium battery - Google Patents
A kind of transient metal sulfide electrode material and preparation method thereof and solid lithium battery Download PDFInfo
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Abstract
The present invention provides a kind of preparation methods of transient metal sulfide electrode material, include the following steps：Metal salt, solvent and sulphur source are mixed, mixed solution is obtained；The metal salt is selected from one of molysite, cobalt salt, nickel salt and vanadic salts or a variety of；The solvent in deionized water, N,N-dimethylformamide, dehydrated alcohol, ethylene glycol, diethylene glycol and glycerine it is any two or more；By the mixed solution thermal response, centrifuge washing after cooling, freeze-drying obtains transient metal sulfide electrode material；The temperature of the thermal response is 120~240 DEG C；Time is 1~36h.The present invention transient metal sulfide electrode material specific discharge capacity with higher and cyclical stability as made under specific condition of experiment.
Description
Technical field
The invention belongs to lithium secondary battery technical field more particularly to a kind of transient metal sulfide electrode material and its systems
Preparation Method and solid lithium battery.
Background technique
Lithium ion battery is due to having many advantages, such as that energy density is high, self-discharge rate is low and has extended cycle life, quotient since 1991
Since industry, it has been widely used in the fields such as consumer electronics and communication.With electric car and scale energy storage
It needs, the battery for developing higher energy density and more preferable safety becomes particularly important.But traditional lithium ion battery is usual
Using combustible organic electrolyte as lithium ion conducting medium, there are the safeties such as inflammable, easy-to-leak liquid and thermal stability difference
Problem, so that the application of lithium ion battery is restricted.Meanwhile active lithium metal can be a series of with liquid electrolyte generation
Side reaction, and in one layer of non-uniform solid electrolyte film of Surface Creation, long circulating will also result in the solid electrolyte film on surface
Cracked or even the case where fall off, lithium anode constantly dissolves.And in charge and discharge process, metal surface out-of-flatness is led
It sends a telegraph current density to be unevenly distributed, will cause Li dendrite and constantly grow and then diaphragm is caused to pierce through, eventually lead to inside battery hair
Raw short circuit.
Solid lithium battery is replaced in conventional lithium ion battery using inorganic solid electrolyte or polymer dielectric
Organic electrolyte has higher safety and better thermal stability, can fundamentally be fully solved conventional lithium ion electricity
The safety issues such as leakage, burning and the explosion in pond.Simultaneously as solid state battery is designed using stack type structure, it is not only simple
Battery structure is changed, but also the energy density of battery can be greatly improved.Inorganic solid electrolyte is mainly solid including sulfide
Body electrolyte and solid oxide electrolyte two major classes.Inorganic solid electrolyte material conductivity at room temperature with higher and
Wide electrochemical window, the conductivity at room temperature of certain sulfide electrolyte is already close to even more than commercialized Organic Electricity
Liquid is solved, and this kind of material has wide electrochemical window, can satisfy the operating voltage range of most electrode materials.Together
When inorganic solid electrolyte be usually ceramics or glass ceramics system, this kind of material mechanical performance also with higher and preferable
Thermal stability can effectively inhibit the growth of Li dendrite, prevent internal short-circuit from causing safety issue, improve solid state battery
Cyclical stability and security performance.Make it possible that lithium metal is applied in battery as negative electrode material, can further mention
The energy density of high battery.And copolymer solid electrolyte is mainly the material system with polyoxyethylene (PEO) for matrix.It is this kind of
The conductivity at room temperature of material is low, and operating temperature range is narrow, while relatively poor to lithium stability, therefore makes actual
With being restricted in the process.
At present commercial Li-ion battery mostly use lithium-containing transition metal oxide and phosphate cathode material (LCO, LMO,
LNO, LFP), this kind of material has high operating voltage and cyclical stability, but specific discharge capacity is usually lower, is unable to satisfy
The requirement of high energy density cells.Meanwhile this kind of material contacted with electrolyte caused by space charge layer will cause high boundary
Face impedance, so that the overall performance of battery declines.Therefore, in solid state battery, how to reduce interface resistance is to improve circulating battery
Stability gives full play to the key point of positive electrode capacity.Transient metal sulfide electrode based on polyelectron reaction has high
Theoretical specific capacity and moderate discharge voltage, can be improved the energy density of battery entirety.Meanwhile transient metal sulfide electrode
There is similar chemical composition and similar chemical potential with sulfide solid electrolyte, therefore not will form space electricity in interface
Lotus layer.However, significantly volume change is generally entailed as positive electrode in charge and discharge process using transient metal sulfide,
This may result in electrode powder or electrode and the case where poor contact occurs in electrolyte contact interface.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of transient metal sulfide electrode material and preparation method thereof and
Solid lithium battery, the electrode material make solid lithium battery specific discharge capacity with higher and cyclical stability.
The present invention provides a kind of preparation methods of transient metal sulfide electrode material, include the following steps：
Metal salt, solvent and sulphur source are mixed, mixed solution is obtained；The metal salt is selected from molysite, cobalt salt, nickel salt and vanadium
One of salt is a variety of；The solvent is selected from deionized water, N,N-dimethylformamide, dehydrated alcohol, ethylene glycol, diethyl two
In pure and mild glycerine it is any two or more；
By the mixed solution thermal response, centrifuge washing after cooling, freeze-drying obtains transient metal sulfide electrode material
Material；
The temperature of the thermal response is 120~240 DEG C；Time is 1~36h.
Preferably, the sulphur source is selected from the one or more of sublimed sulfur, thioacetamide, thiocarbamide and L-cysteine.
Preferably, the solvent be selected from the mixed solvent of n,N-Dimethylformamide and ethylene glycol, dehydrated alcohol and go from
The mixed solvent of the mixed solvent of sub- water, the mixed solvent of deionized water and glycerine or deionized water and diethylene glycol.
Preferably, described to mix metal salt, solvent and sulphur source, it obtains mixed solution and specifically includes：
Metal salt and solvent are mixed, stirs to being completely dissolved, obtains metal salt solution；
The metal salt solution and sulphur source are mixed, stirs to being completely dissolved, obtains mixed solution.
Preferably, the temperature of the freeze-drying is -35 DEG C~-55 DEG C；The time of freeze-drying is 12~36h.
Preferably, the molar concentration of metal salt is 0.01mmol/L~1mol/L in the mixed solution；The sulphur source
Molar concentration is 0.01mmol/L~5mmol/L.
Preferably, the pattern of the transient metal sulfide electrode material is selected from nano particle, nanometer rods, nanometer sheet, receives
Mitron, micron solid ball or tiny balloon.
The present invention provides a kind of solid state lithium batteries, including anode, cathode and are arranged between the anode and cathode
Solid electrolyte；
The just extremely transient metal sulfide electrode material of the preparation of preparation method described in above-mentioned technical proposal.
Preferably, the solid electrolyte is electrolysed selected from binary solid electrolyte-tertiary solid electrolyte two-layer solid-state
Matter；Wherein, binary solid electrolyte is selected from Li3PS4、75Li2S-24P2S5-1P2O5、90Li3PS4-10ZnO、77.5Li2S-
22.5P2S5、Li7P3S11、75Li2S·25P2S5、70Li2S-29P2S5-1Li3PO4、70Li2S-29P2S5-1P2S3Or 80Li2S-
20P2S5；
The tertiary solid electrolyte is selected from Li10GeP2S12、Li2S-GeS2-P2S5、Li2S-SiS2-P2S5、Li2S-SnS2-
P2S5Or Li2S-Al2S3-P2S5。
The present invention provides a kind of preparation methods of transient metal sulfide electrode material, include the following steps：By metal
Salt, solvent and sulphur source mixing, obtain mixed solution；The metal salt is selected from one of molysite, cobalt salt, nickel salt and vanadic salts or more
Kind；The solvent is appointed in deionized water, N,N-dimethylformamide, dehydrated alcohol, ethylene glycol, diethylene glycol and glycerine
Anticipate two or more；By the mixed solution thermal response, centrifuge washing after cooling, freeze-drying obtains transient metal sulfide
Electrode material；The temperature of the thermal response is 120~240 DEG C；Time is 1~36h.The present invention passes through under specific condition of experiment
Transient metal sulfide electrode material obtained specific discharge capacity with higher and cyclical stability.The experimental results showed that：?
Ferrous disulfide electrode material still has the reversible specific capacity close to 1000mAh/g under 100mA/g current density after recycling 50 weeks；?
Cobalt disulfide electrode material still has the reversible specific capacity close to 600mAh/g under 1000mA/g current density after recycling 50 weeks；?
Still there is after recycling 100 weeks close to the reversible of 700mAh/g the curing nickel electrode material of hollow ball-shape under 500mA/g current density
Specific capacity；Four vanadic sulfide electrode materials still have the reversible ratio close to 570mAh/g under 500mA/g current density after recycling 50 weeks
Capacity.
Detailed description of the invention
Fig. 1 is the XRD spectra of ferrous disulfide electrode material prepared by the embodiment of the present invention 1；
Fig. 2 is the SEM figure of ferrous disulfide electrode material prepared by the embodiment of the present invention 1；
Fig. 3 is the charging and discharging curve figure of ferrous disulfide electrode material prepared by the embodiment of the present invention 1；
Fig. 4 is the SEM figure of curing nickel electrode material prepared by the embodiment of the present invention 3.
Specific embodiment
The present invention provides a kind of preparation methods of transient metal sulfide electrode material, include the following steps：
Metal salt, solvent and sulphur source are mixed, mixed solution is obtained；The metal salt is selected from molysite, cobalt salt, nickel salt and vanadium
One of salt is a variety of；The solvent is selected from deionized water, N,N-dimethylformamide, dehydrated alcohol, ethylene glycol, diethyl two
In pure and mild glycerine it is any two or more；
By the mixed solution thermal response, centrifuge washing after cooling, freeze-drying obtains transient metal sulfide electrode material
Material；
The temperature of the thermal response is 120~240 DEG C；Time is 1~36h.
The present invention prepares transient metal sulfide electrode material, the S that sulphur source slowly releases using solvent thermal process2 2-With
Metal cation reacts, and by control reaction temperature and time, obtains transient metal sulfide electrode material.The metal sulphur
Compound electrode material can be improved the specific discharge capacity and cyclical stability of solid state lithium battery, on the one hand based on polyelectron reaction
Transient metal sulfide theoretical specific capacity with higher and moderate operating voltage, it is solid applied to can be improved in solid state battery
The energy density of state battery；On the other hand, transient metal sulfide electrode material can increase connecing for electrode and solid electrolyte
Contacting surface product, while alleviating the bulk effect in cyclic process, improve the cycle life of solid state battery.
The present invention mixes metal salt, solvent and sulphur source, obtains mixed solution.In the present invention, it is described by metal salt, it is molten
Agent and sulphur source mixing, obtain mixed solution and specifically preferably include：
Metal salt and solvent are mixed, stirs to being completely dissolved, obtains metal salt solution；
The metal salt solution and sulphur source are mixed, stirs to being completely dissolved, obtains mixed solution.
The present invention mixes metal salt and solvent, stirs to being completely dissolved, obtains metal salt solution.In the present invention, institute
It states metal salt and is preferably selected from one of molysite, cobalt salt, nickel salt and vanadic salts or a variety of.It is described in the specific embodiment of the invention
Metal salt is chosen in particular from FeSO4·7H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O and NH4VO3One of or it is a variety of.
In the present invention, the solvent is selected from deionized water, n,N-Dimethylformamide, dehydrated alcohol, ethylene glycol, diethyl
In two pure and mild glycerine it is any two or more；It is preferably selected from the mixed solvent, anhydrous of N,N-dimethylformamide and ethylene glycol
The mixing of the mixed solvent or deionized water and diethylene glycol of ethyl alcohol and the mixed solvent of deionized water, deionized water and glycerine
Solvent.In the specific embodiment of the invention, it is 4 that the solvent, which is selected from volume ratio,:3 N,N-dimethylformamide and ethylene glycol
Mixed solvent；Volume ratio is 1:1 dehydrated alcohol and the mixed solvent of deionized water；Volume ratio is 6:1 deionized water and third
The mixed solvent or volume ratio of triol are 6:2 deionized water and the mixed solvent of diethylene glycol.
After obtaining metal salt solution, the present invention mixes the metal salt solution and sulphur source, stirs to being completely dissolved, obtains
Mixed solution.In the present invention, the sulphur source is preferably selected from one kind of sublimed sulfur, thioacetamide, thiocarbamide and L-cysteine
Or it is a variety of.
In the present invention, the molar concentration of metal salt is limited to 0.01mmol/L~1mol/L in the mixed solution, more
Preferably 0.01~100mmol/L；The molar concentration of the sulphur source is preferably 0.01mmol/L~5mmol/L, more preferably
0.05mmol/L~500mmol/L.
After obtaining mixed solution, the present invention is by the mixed solution thermal response, centrifuge washing after cooling, and freeze-drying obtains
To transient metal sulfide electrode material.In the present invention, the temperature of the thermal response be 120~240 DEG C, preferably 160~
200℃；The time of thermal response is 1~36h, preferably 8~20h.
The present invention is centrifuged after being preferably cooled to room temperature, to centrifugation product washing.The temperature of the freeze-drying is preferably -35
DEG C~-55 DEG C, more preferably -40~-50 DEG C；The time of freeze-drying is preferably 12~36h, more preferably 20~30h.
The present invention is preferably selected from nanometer by control experiment condition, the pattern of obtained transient metal sulfide electrode material
Particle, nanometer rods, nanometer sheet, nanotube, micron solid ball or tiny balloon.The above-mentioned transition metal with certain microscopic appearance
Sulfide electrode material can alleviate volume change, increase the contact area of active material and solid electrolyte.
In the present invention, the transient metal sulfide is preferably specially ferrous disulfide, ferriferrous sulfide, eight vulcanizations seven
Iron, cobalt disulfide, cobaltosic sulfide, curing nickel, four three nickel of vulcanization, vanadium disulfide, four vanadic sulfides or eight five vanadium of vulcanization.
The present invention provides a kind of solid state lithium batteries, including anode, cathode and are arranged between the anode and cathode
Solid electrolyte；
The just extremely transient metal sulfide electrode material of the preparation of preparation method described in above-mentioned technical proposal.
In the present invention, the solid lithium battery pack includes anode, the transition gold of the just extremely described preparation method preparation
Belong to sulfide electrode material.
In the present invention, the solid lithium battery pack includes cathode, and the cathode is lithium metal.
In the present invention, the solid lithium battery pack includes the solid electrolyte being arranged between the anode and cathode.Institute
It states solid electrolyte and is preferably selected from binary solid electrolyte-tertiary solid electrolyte two-layer solid-state electrolyte；Wherein, binary is solid
Body electrolyte is preferably selected from Li3PS4、75Li2S-24P2S5-1P2O5、90Li3PS4-10ZnO、77.5Li2S-22.5P2S5、
Li7P3S11、75Li2S·25P2S5、70Li2S-29P2S5-1Li3PO4、70Li2S-29P2S5-1P2S3Or 80Li2S-20P2S5；Institute
It states tertiary solid electrolyte and is preferably selected from Li10GeP2S12、Li2S-GeS2-P2S5、Li2S-SiS2-P2S5、Li2S-SnS2-P2S5Or
Li2S-Al2S3-P2S5.In the specific embodiment of the invention, the solid-state conductive medium is Li10GeP2S12- 75%Li2S24%
P2S51%P2O5Two-layer solid-state electrolyte, Li10GeP2S12- 70%Li2S29%P2S51%Li3PO4Two-layer solid-state electrolysis
Matter, Li10GeP2S12- 75%Li2S25%P2S5Two-layer solid-state electrolyte or Li10GeP2S12- 80%Li2S20%P2S5It is double
Layer solid electrolyte.
Anode of the transient metal sulfide electrode material prepared by the present invention as solid lithium battery, due to transition metal
Sulfide electrode has preferable interface compatibility and stability and special microscopic appearance to electrolyte, and makes all solid lithium
Battery specific discharge capacity with higher and cyclical stability.
In order to further illustrate the present invention, below with reference to embodiment to a kind of transient metal sulfide electricity provided by the invention
The preparation method and applications of pole material are described in detail, but they cannot be interpreted as to the limit to the scope of the present invention
It is fixed.
Embodiment 1
By the FeSO of 4mmol4·7H2O is added to 40mL N,N-dimethylformamide and the ethylene glycol mixed solvent of 30mL
In, 1.0h is stirred at room temperature to being completely dissolved, obtains mixed solution；Urea is then added to above-mentioned in the mixed solvent magnetic agitation
0.5h finally, being added thereto 20mmol sublimed sulfur under argon atmosphere protection, and reacts 8h at 180 DEG C in three-neck flask, will
Black precipitate centrifuge washing obtains ferrous disulfide electrode material after being freeze-dried for 24 hours at -40 DEG C.
Fig. 1 is the XRD spectra of ferrous disulfide electrode material prepared by the embodiment of the present invention 1；Fig. 1 shows：It is prepared by embodiment 1
Electrode material be pure phase ferrous disulfide.
The ferrous disulfide electrode material that the present invention prepares embodiment 1 is scanned Electronic Speculum test, as a result sees that Fig. 2, Fig. 2 are
The SEM figure of ferrous disulfide electrode material prepared by the embodiment of the present invention 1；As can be seen from Figure 2：Curing prepared by embodiment 1
The sphere that iron electrode material microscopic appearance is about 1 μm of diameter.
With Li10GeP2S12- 75%Li2S24%P2S51%P2O5Two-layer solid-state electrolyte is as conducting medium, metal
Lithium is assembled into solid lithium battery as cathode, carries out multiplying power and cycle performance test at room temperature.100mA/g,
Under 500mA/g, 1000mA/g and 5000mA/g current density after 50 circle of circulation, FeS2Micron ball release respectively 997.2mAh/g,
The specific capacity of 839.7mAh/g, 717.0mAh/g and 666.8mAh/g.
Fig. 3 is the charging and discharging curve figure of ferrous disulfide electrode material prepared by the embodiment of the present invention 1；As can be seen from Figure 3, exist
Recycled 50 weeks under 100mA/g current density, embodiment 1 prepare ferrous disulfide electrode material still have close to 1000mAh/g can
Inverse specific capacity.
Embodiment 2
By the Co (NO of 0.1mmol3)2·6H2O and 0.5mmol thioacetamide be added to simultaneously 40mL dehydrated alcohol and
40mL deionized water in the mixed solvent, room temperature magnetic agitation 1.0h to be uniformly mixed.It is then transferred into reaction kettle at 160 DEG C anti-
12h is answered, after naturally cooling to room temperature, by black precipitate centrifuge washing, freeze-drying for 24 hours, obtains cobalt disulfide electrode material,
Microscopic appearance is the cobalt disulfide electrode material of nano particle.
With Li10GeP2S12- 70%Li2S29%P2S51%Li3PO4Two-layer solid-state electrolyte is as conducting medium, gold
Belong to lithium as cathode and be assembled into solid lithium battery, carries out multiplying power and cycle performance test at room temperature.100mAh/g,
Under 200mAh/g, 500mAh/g and 1000mA/g current density after 50 circle of circulation, CoS2Nano particle releases 887.5mAh/ respectively
G, the specific capacity of 799.2mAh/g, 702.8mAh/g and 596.8mAh/g.Meanwhile it being recycled 50 weeks under 1000mA/g current density
Still there is the reversible specific capacity close to 600mAh/g.
Embodiment 3
By the Ni (NO of 1mmol3)2·6H2O is added to the deionized water and 10mL glycerine in the mixed solvent of 60mL, room temperature
Stirring 1.0h obtains mixed solution to being completely dissolved；Then 1mmol thiocarbamide and 4mmolL- cysteine are added to above-mentioned mixed
Magnetic agitation 1h in bonding solvent.12h is reacted finally, above-mentioned solution is transferred in reaction kettle at 160 DEG C.After being cooled to room temperature,
By black precipitate centrifuge washing, it is freeze-dried at -40 DEG C and obtains curing nickel electrode material afterwards for 24 hours.
Fig. 4 is the SEM figure of curing nickel electrode material prepared by the embodiment of the present invention 3, and Fig. 4 can be seen that：Embodiment 3 is made
Standby product is the curing nickel electrode material that microscopic appearance is about 1 μm of hollow ball-shape of diameter.
With Li10GeP2S12- 75%Li2S25%P2S5Two-layer solid-state electrolyte is as conducting medium, and lithium metal is as negative
Pole is assembled into solid lithium battery, carries out multiplying power and cycle performance test at room temperature.In 100,200,500 and
Under 1000mA/g current density after 50 circle of circulation, NiS2Hollow sphere releases 868.3,789.4,712.8 and 636.8mAh/g respectively
Specific capacity.100 weeks reversible specific capacities still having close to 700mAh/g are recycled under 500mA/g current density.
Embodiment 4
The NH of 1.5g4VO3It is added to the deionized water and 20mL diethylene glycol in the mixed solvent of 60mL, 1.0h is stirred at room temperature
To being completely dissolved, mixed solution is obtained；3.0g thioacetamide is then added to above-mentioned in the mixed solvent magnetic agitation 0.5h,
20h is reacted finally, above-mentioned solution is transferred in reaction kettle at 160 DEG C, after being cooled to room temperature, by black precipitate centrifuge washing ,-
It is freeze-dried at 40 DEG C and obtains four vanadic sulfide electrode materials afterwards for 24 hours.Microscopic appearance is about 5 microns of diameter spherical four vanadic sulfides electricity
Pole material.
With Li10GeP2S12- 80%Li2S20%P2S5Two-layer solid-state electrolyte is as conducting medium, and lithium metal is as negative
Pole is assembled into solid lithium battery, carries out multiplying power and cycle performance test at room temperature.In 100,200,500 and
Under 1000mA/g current density after 20 circle of circulation, VS4Micron ball releases 758.3,676.4,608.4 and 529.1mAh/g's respectively
Specific capacity.50 weeks reversible specific capacities still having close to 570mAh/g are recycled under 500mA/g current density.
Comparative example 1
By 1.35g FeCl3·6H2O is added in 10mL deionized water, and 1.0h is stirred at room temperature to being completely dissolved, is mixed
Close solution；0.38g urea is then added to above-mentioned in the mixed solvent magnetic agitation for a period of time.Above-mentioned mixed solution is shifted
180 DEG C of reaction 12h into reaction kettle.By black precipitate centrifuge washing, ferrous disulfide electrode material is obtained after being freeze-dried 10h.
Using commercialized organic electrolyte as conducting medium, lithium metal is assembled into button cell as cathode, in room temperature
Under the conditions of carry out multiplying power and cycle performance test.Charge and discharge 100 weeks under 100mA/g, specific discharge capacity only has 220mAh/g or so.
Comparative example 2
By 2mmolCoCl2·6H2O is dissolved completely in 70mL dehydrated alcohol, and blue solution is then transferred to reaction kettle
In.10mmol sublimed sulfur stirring a period of time is then added.It is reacted for 24 hours at 240 DEG C.After being cooled to room temperature, precipitating centrifugation is washed
It washs, vacuum drying obtains CoS2Micrometre hollow sphere.
Using organic electrolyte as conducting medium, lithium metal is assembled into button cell as cathode, at room temperature into
Row multiplying power and cycle performance test.After circulation 10 times, specific capacity is only left 530mAh/g, and cycle performance and high rate performance are obvious
Lower than solid state battery.And there are the security risks of leakage, burning and explosion using organic electrolyte.
Comparative example 3
0.6g PVP K-30 is dissolved in 40mL ethylene glycol and 40mL deionized water mixed solution.2mmol's
C4H6O4Ni·4H2The Na of O and 6mmol2S2O3·5H2O is continuously stirred to be dissolved in above-mentioned solution and is finally shifted above-mentioned mixed solution
180 DEG C of heat preservation 12h are heated into hydrothermal reaction kettle.After temperature drops to room temperature, by black precipitate centrifuge washing, vacuum drying
Afterwards, curing nickel nanosphere is obtained.
Using organic electrolyte as conducting medium, lithium metal is as button cell is assembled into cathode, at room temperature
Electrochemical property test is carried out, its multiplying power and cycle performance are tested, after recycling 50 times, reversible specific capacity 472mAh/g, capacity
Decaying is obvious.
As seen from the above embodiment, the present invention provides a kind of preparation method of transient metal sulfide electrode material, packets
Include following steps：Metal salt, solvent and sulphur source are mixed, mixed solution is obtained；The metal salt is selected from molysite, cobalt salt, nickel salt
With one of vanadic salts or a variety of；The solvent is selected from deionized water, N,N-dimethylformamide, dehydrated alcohol, ethylene glycol, two
In ethylene glycol and glycerine it is any two or more；By the mixed solution thermal response, centrifuge washing after cooling, freeze-drying,
Obtain transient metal sulfide electrode material；The temperature of the thermal response is 120~240 DEG C；Time is 1~36h.The present invention is logical
Cross the specific discharge capacity with higher of the transient metal sulfide electrode material obtained under specific condition of experiment and stable circulation
Property.The experimental results showed that：Ferrous disulfide electrode material still has after recycling 50 weeks close to 1000mAh/ under 100mA/g current density
The reversible specific capacity of g；Cobalt disulfide electrode material still has after recycling 50 weeks close to 600mAh/g under 1000mA/g current density
Reversible specific capacity；The curing nickel electrode material of hollow ball-shape still has close after recycling 100 weeks under 500mA/g current density
The reversible specific capacity of 700mAh/g；Four vanadic sulfide electrode materials still have close after recycling 50 weeks under 500mA/g current density
The reversible specific capacity of 570mAh/g.
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 (10)
1. a kind of preparation method of transient metal sulfide electrode material, includes the following steps：
Metal salt, solvent and sulphur source are mixed, mixed solution is obtained；The metal salt is in molysite, cobalt salt, nickel salt and vanadic salts
It is one or more；The solvent be selected from deionized water, N,N-dimethylformamide, dehydrated alcohol, ethylene glycol, diethylene glycol and
In glycerine it is any two or more；
By the mixed solution thermal response, centrifuge washing after cooling, freeze-drying obtains transient metal sulfide electrode material；
The temperature of the thermal response is 120~240 DEG C；Time is 1~36h.
2. preparation method according to claim 1, which is characterized in that the sulphur source is selected from sublimed sulfur, thioacetamide, sulphur
Urea and L-cysteine it is one or more.
3. preparation method according to claim 1, which is characterized in that the solvent is selected from n,N-Dimethylformamide and second
The mixed solvent of glycol, the mixed solvent of dehydrated alcohol and deionized water, deionized water and glycerine mixed solvent or go from
The mixed solvent of sub- water and diethylene glycol.
4. preparation method according to claim 1, which is characterized in that the metal salt is selected from FeSO4·7H2O、Co
(NO3)2·6H2O、Ni(NO3)2·6H2O and NH4VO3One of or it is a variety of.
5. preparation method according to claim 1, which is characterized in that it is described to mix metal salt, solvent and sulphur source, it obtains
Mixed solution specifically includes：
Metal salt and solvent are mixed, stirs to being completely dissolved, obtains metal salt solution；
The metal salt solution and sulphur source are mixed, stirs to being completely dissolved, obtains mixed solution.
6. transient metal sulfide electrode material according to claim 1, which is characterized in that the temperature of the freeze-drying
It is -35 DEG C~-55 DEG C；The time of freeze-drying is 12~36h.
7. preparation method according to claim 1, which is characterized in that the molar concentration of metal salt is in the mixed solution
0.01mmol/L~1mol/L；The molar concentration of the sulphur source is 0.01mmol/L~5mmol/L.
8. preparation method according to claim 1, which is characterized in that the pattern of the transient metal sulfide electrode material
Selected from nano particle, nanometer rods, nanometer sheet, nanotube, micron solid ball or tiny balloon.
9. a kind of solid state lithium battery, including anode, cathode and the solid electrolyte being arranged between the anode and cathode；
The just extremely transient metal sulfide electrode material of any one of claim 1~8 preparation method preparation.
10. solid state lithium battery according to claim 9, which is characterized in that the solid electrolyte is selected from binary solid electricity
Solve matter-tertiary solid electrolyte two-layer solid-state electrolyte；Wherein, binary solid electrolyte is selected from Li3PS4、75Li2S-
24P2S5-1P2O5、90Li3PS4-10ZnO、77.5Li2S-22.5P2S5、Li7P3S11、75Li2S·25P2S5、70Li2S-
29P2S5-1Li3PO4、70Li2S-29P2S5-1P2S3Or 80Li2S-20P2S5；
The tertiary solid electrolyte is selected from Li10GeP2S12、Li2S-GeS2-P2S5、Li2S-SiS2-P2S5、Li2S-SnS2-P2S5
Or Li2S-Al2S3-P2S5。
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