CN105098228A - Sulfide solid electrolyte material and preparation method thereof - Google Patents
Sulfide solid electrolyte material and preparation method thereof Download PDFInfo
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- CN105098228A CN105098228A CN201410188063.4A CN201410188063A CN105098228A CN 105098228 A CN105098228 A CN 105098228A CN 201410188063 A CN201410188063 A CN 201410188063A CN 105098228 A CN105098228 A CN 105098228A
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Abstract
The invention provides a sulfide solid electrolyte material and a preparation method thereof. The preparation method comprises the following steps: mixing Li2S, P2S5 and M2Sn with an organic solvent to obtain a suspension liquid; sequentially stirring, dissolving, crystallizing, centrifuging, filtering and drying the suspension liquid; and then carrying out thermal treatment, so as to obtain the sulfide solid electrolyte material. Compared with the prior art, a compound containing Li, P, M and S is formed in an organic solution; the compound and a little of organic solvent form a crystalline state; the residual organic solvent in the suspension liquid is separated and volatilized in the centrifuging, separating and drying processes; meanwhile, most of crystalline-state solvent is also separated and volatilized; and nanopores are left by the residual solvent and the crystalline-state solvent in solid electrolyte in the volatilizing process. Due to the presence of the nanopores, the specific surface area of the sulfide solid electrolyte material is increased; and meanwhile, the material particles are relatively small, and easy to compact, therefore, the ionic conductivity of the sulfide solid electrolyte material is increased.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to sulfide solid electrolyte material and preparation method thereof.
Background technology
Current, lithium secondary battery is widely applied in daily life, becomes the part that society is indispensable.Lithium secondary battery has that power output is large, energy density is high, long service life, average output voltage are high, self discharge is little, memory-less effect, can fast charging and discharging, cycle performance superior to advantages such as non-environmental-pollutions, become now for the first choice of the rechargable power supplies of portable type electronic product, be also considered to the Vehicular dynamic battery of most competitiveness.Lithium secondary battery is divided into liquid lithium secondary cell and solid lithium secondary cell.Wherein, solid lithium secondary cell refers to that each unit of battery comprises positive pole, negative pole and electrolyte, and all adopt the lithium secondary battery of solid-state material, therefore solid lithium secondary cell is also known as all solid lithium secondary battery.Because all solid lithium secondary battery has the incomparable high security of liquid lithium secondary cell, and be expected to the potential safety hazard thoroughly eliminated in use procedure, more meet the demand of electric automobile and scale energy storage field future development.
Up to now, the research and development that solid lithium battery topmost bottleneck practical is on a large scale high-performance solid electrolyte are limited.Sulfide solid electrolyte, owing to having high ionic conductivity and wide electrochemical window, is a kind of inorganic solid electrolyte material that can be advantageously applied to all solid lithium secondary battery.Develop multiple sulfide solid electrolyte material at present, such as, publication number is the preparation method that the Chinese patent of CN101326673A discloses a kind of lithium ion conducting sulfide based solid electrolyte material, and the room temperature lithium ion conductivity of this sulfide-based solid electrolyte material reaches about 10
-3scm
-1, its manufacture process first at high temperature obtains chalcogenide glass, and then at high temperature heat treatment obtains chalcogenide glass pottery, and whole manufacture process needs inert atmosphere protection.Although the ionic conductivity of the sulfide-based dielectric substance of above-mentioned patent is relatively high, manufacture method is complicated thus significantly increase cost, not easily carries out industrial-scale production.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of sulfide solid electrolyte material and preparation method thereof, and sulfide solid electrolyte material preparation method provided by the invention is simple, and the sulfide solid electrolyte material ionic conductivity of preparation is higher.
The invention provides the sulfide solid electrolyte material shown in a kind of formula (I):
xLi
2S·yP
2S
5·zM
2S
n(I)；
Wherein, x+y+z=100%; M is one or more in Al, Ge, Ti and La; N is the chemical valence of M.
Preferably, the span of described x is 40% ~ 80%.
Present invention also offers a kind of preparation method of sulfide solid electrolyte material, comprise the following steps:
A) by Li
2s, P
2s
5, M
2s
nmix with organic solvent, obtain suspension; Li
2s, P
2s
5with M
2s
nmol ratio be x:y:z;
B) by described mixed solution successively through stirring-reaction, centrifugal, filter with drying after, obtain at the beginning of expect;
C) described just material is heat-treated, obtain the sulfide solid electrolyte material shown in formula (I);
xLi
2S·yP
2S
5·zM
2S
n(I)；
Wherein, x+y+z=100%; M is one or more in Al, Ge, Ti and La; N is the chemical valence of M.
Preferably, described organic solvent is selected from one or more in alcohols solvent, ether solvent and nitrile solvents.
Preferably, described organic solvent is selected from one or more in ethanol, propyl alcohol, penta hexanol, ether, acetonitrile and oxolane.
Preferably, the water content of described organic solution is less than 1wt%.
Preferably, the speed of described stirring is 30rpm ~ 800rpm, and the time of described stirring is 10h ~ 80h; Described centrifugal rotating speed is 3000rpm ~ 20000rpm, and the described centrifugal time is 0 ~ 60min; The time of described drying is 0 ~ 20h, and the temperature of described drying is 60 DEG C ~ 200 DEG C.
Preferably, described heat treated temperature is 200 DEG C ~ 700 DEG C, and the described heat treated time is 0.5h ~ 10h.
Preferably, described mixing, stirring-reaction, centrifugal, filter, dry and heat treatment carries out all be less than the environment of 10% in humidity under.
Preferably, described mixing, stirring-reaction, centrifugal, filter, dry and heat treatment carries out independently of one another under the condition of closed environment or inert gas shielding.
The invention provides a kind of sulfide solid electrolyte material and preparation method thereof, this preparation method comprises the following steps: A) by Li
2s, P
2s
5, M
2s
nmix with organic solvent, obtain suspension; Li
2s, P
2s
5with M
2s
nmol ratio be x:y:z; B) by described mixed solution successively through stirring-reaction, centrifugal, filter with drying after, obtain at the beginning of expect; C) described just material is heat-treated, obtain the sulfide solid electrolyte material shown in formula (I).Compared with prior art, the present invention in the process preparing sulfide solid electrolyte material, by Li
2s, P
2s
5with M
2s
nreact in organic solution, Li
2s, P
2s
5with M
2s
nformed in organic solution containing Li, P, the compound of M and S, this compound and a small amount of organic solvent can form crystalline state, organic solvent residual in suspension is separated and volatilization in centrifugation and drying course, simultaneously most of crystalline state solvent also can separated and volatilization, residual solvent and crystalline state solvent are in volatilization process, nanoaperture is left in solid electrolyte, the existence of nanoaperture not only increases the specific area of sulfide solid electrolyte material, make sulfide solid electrolyte material particle comparatively fine and smooth simultaneously, be easy to compacting densification, thus increase its ionic conductivity.From said process, sulfide solid electrolyte material preparation process of the present invention is simple, only needs Li
2s, P
2s
5with M
2s
nbe mixed in organic solution, then through stirring-reaction, centrifugal, filter and heat treatment, can sulfide solid electrolyte material be obtained, and at room temperature can complete the preparation of sulfide electrolyte material.
Experimental result shows, the ionic conductivity under sulfide solid electrolyte material room temperature provided by the invention is close to 10
-2scm
-1.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet that the embodiment of the present invention 1 prepares sulfide solid electrolyte material;
Fig. 2 is the X ray diffracting spectrum of sulfide solid electrolyte material prepared by the embodiment of the present invention 1;
Fig. 3 is the loose structure micrograph of sulfide solid electrolyte material prepared by the embodiment of the present invention 1;
Fig. 4 is the AC impedance spectrogram of sulfide solid electrolyte material when room temperature prepared by the embodiment of the present invention 1;
Fig. 5 is sulfide solid electrolyte material ionic conductivity curve chart at different temperatures prepared by the embodiment of the present invention 1;
Fig. 6 is the chronoamperometry curve chart of sulfide solid electrolyte material prepared by the embodiment of the present invention 1;
Fig. 7 is the Raman spectrogram of sulfide solid electrolyte material prepared by the embodiment of the present invention 1;
Fig. 8 is the sulfide solid electrolyte material of employing embodiment 1 is the first charge-discharge curve chart of electrolytical solid lithium battery when 0.5C.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
Solid Li
2s, solid P
2s
5with sulfide M
2s
ncan interreaction when high temperature, form the xLi containing Li, P, M and S
2syP
2s
5zM
2s
nsulfide solid electrolyte.Solid Li
2s, solid P
2s
5with sulfide M
2s
nduring contact, by spreading mutually between atom, the xLi lower relative to reactant energy can be generated
2syP
2s
5zM
2s
nsolid electrolyte material, under normal temperature, nuclear energy is lower, is difficult to overcome diffusion barrier, and therefore atoms permeating is slowly; By solid Li
2s, solid P
2s
5with sulfide M
2s
nbe heated to higher temperature, nuclear energy increases, and can overcome diffusion barrier, and atomic diffusion rates is accelerated, and finally forms xLi
2syP
2s
5zM
2s
nsulfide solid electrolyte, and the xLi formed at different conditions
2syP
2s
5zM
2s
nthe composition Structure and Properties of sulfide solid electrolyte is different.
Applicant finds, by Li through research
2s, P
2s
5with M
2s
nwhen being mixed in part organic solution, Li
2s, P
2s
5with M
2s
norganic solvent can be partially soluble in, because the energy of product is low, its solubility is in a solvent less than the solubility of reactant, therefore, solution is oversaturated for product, can separate out crystalline product, and reactant constantly dissolves, until react completely, thus simplify the preparation process of sulfide electrolyte material, but select suitable organic solution to be the difficult point realizing preparation sulfide electrolyte material.
This application provides the sulfide solid electrolyte material shown in a kind of formula (I) thus:
xLi
2S·yP
2S
5·zM
2S
n(I)；
Wherein, x+y+z=100%; M is one or more in Al, Ge, Ti and La; N is the chemical valence of M.The span of described x is preferably 40% ~ 80%, is more preferably 50% ~ 80%, then is preferably 60% ~ 80%; The span of described y is preferably 10% ~ 30%, is more preferably 10% ~ 20%; The span of described z is preferably 10% ~ 30%, is more preferably 10% ~ 20%.
Present invention also offers the preparation method of the sulfide solid electrolyte material shown in above-mentioned formula (I), comprise the following steps:
A) by Li
2s, P
2s
5, M
2s
nmix with organic solvent, obtain mixed solution; Li
2s, P
2s
5with M
2s
nmol ratio be x:y:z;
B) by described mixed solution successively through stirring-reaction, centrifugal, filter with drying after, obtain at the beginning of expect;
C) described just material is heat-treated, obtain the sulfide solid electrolyte material shown in formula (I);
xLi
2S·yP
2S
5·zM
2S
n(I)；
Wherein, x+y+z=100%; M is one or more in Al, Ge, Ti and La; N is the chemical valence of M.Described x, y and z are all same as above, do not repeat them here.
The restriction that the present invention is not special to the source of all raw materials, for commercially available.
In the process preparing sulfide solid electrolyte material, what first carry out is the mixed process of raw material, by Li
2s, P
2s
5, M
2s
nmix with organic solution, obtain suspension, also can be described as first and just expect.The mode of the present invention to described mixing has no particular limits, and can be artificial mixing or mechanical mixture, the application be preferably mechanical mixture.Described Li
2s, P
2s
5, M
2s
njust simply mix with mixing of organic solution, chemical reaction does not occur.
According to the present invention, described organic solution is preferably alcohols that chemical formula is R-OH, chemical formula is R
1-O-R
2ethers and chemical formula be R
3one or more in the nitrile of-C ≡ N, wherein, R, R
1, R
2and R
3independently be preferably hydrocarbon system separately or containing heteroatomic hydrocarbon system, be more preferably alkane or contain heteroatomic alkane.Described organic solution be more preferably in ethanol, propyl alcohol, penta hexanol, ether, acetonitrile and oxolane one or more, then be preferably acetonitrile or oxolane.The water content of described organic solution is preferably less than 1wt%, if the water content of organic solution is too much, then and Li
2s, P
2s
5with M
2s
neasy generation side reaction-hydrolysis, produces hydrogen sulfide, thus affects the performance of sulfide electrolyte material.
By described Li
2s, P
2s
5, M
2s
nafter mixing with organic solvent, then just expect described first to stir, obtain just expecting with second of white precipitate.Li during described stirring makes first just to expect
2s, P
2s
5with M
2s
ncontact is fully reaction also, and the described second first material is that the chemical formula of sulfide electrolyte material can use [xLi with the sulfide solid electrolyte material of recrystallisation solvent and the mixed solution of solvent
2syP
2s
5zM
2s
nsolvent] represent.Stirring of the present invention is preferably mechanical agitation, and the present invention is not particularly limited described mechanical agitation, and described mechanical agitation speed is preferably 30rpm ~ 800rpm, is more preferably 400rpm ~ 600rpm; The time of described stirring is preferably 10h ~ 80h, is more preferably 12h ~ 48h, most preferably is 12h ~ 24h.
According to the present invention, stir after terminating, just expect described second to carry out centrifugation, obtain the 3rd and just expect.3rd just expects that top is frivolous liquid, and bottom is white precipitate.Part organic solvent in second just material is separated and volatilization with partial solvent crystalline solid by described centrifugation, obtain the 3rd just to expect, described 3rd just material be the mixture with the sulfide solid electrolyte material of recrystallisation solvent, sulfide solid electrolyte material and a small amount of solvent, it be the solid of humidity.The present invention has no particular limits described centrifugation, and described centrifugal rotating speed is preferably 3000rpm ~ 20000rpm, is more preferably 5000rpm ~ 16000rpm, most preferably is 8000rpm ~ 12000rpm; The described centrifugal time is preferably 0 ~ 60min, is more preferably 0 ~ 30min, then is preferably 0 ~ 15min, most preferably is 5 ~ 15min.
After described centrifugal end, just expect the described 3rd to filter, obtain the 4th and just expect.The present invention has no particular limits described filtration, can be suction filtration well known to those skilled in the art also can be press filtration.
According to the present invention, after described filter process terminates, just expect to carry out drying to the 4th, obtain the 5th and just expect.A small amount of organic solvent in 4th just material can volatilize by described drying completely, obtains the 5th and just expects.Described 5th just expects to be with the sulfide solid electrolyte material of recrystallisation solvent and the mixture of sulfide solid electrolyte material, and it is dry solid.The present invention has no particular limits described drying mode, and the time of described drying is preferably 0 ~ 20h, is more preferably 2 ~ 10h, most preferably is 4 ~ 8h, and the temperature of described drying is preferably 60 DEG C ~ 200 DEG C, is more preferably 60 DEG C ~ 100 DEG C.
Finally just expect the 5th to heat-treat, volatilize in the 5th just material completely with the crystallization of the sulfide solid electrolyte material of recrystallisation solvent, thus obtain sulfide solid electrolyte material.The present invention has no particular limits described heat treated mode, described heat treated temperature is preferably 200 DEG C ~ 700 DEG C, is more preferably 500 DEG C ~ 700 DEG C, then is preferably 550 DEG C ~ 700 DEG C, the described heat treated time is preferably 0.5 ~ 10h, is more preferably 0.5 ~ 5h.
In order to avoid at Li
2s, P
2s
5with M
2s
nside reaction is there is in course of reaction, the present invention preferably to described mixing, stirring, centrifugal, filter, environment that is dry and heat treatment process limits, carry out preferably be less than the environment of 10% in humidity under, more preferably carry out under closed environment or inert gas shielding, more preferably to carry out under the condition of inert gas shielding; Described inert gas is inert gas well known to those skilled in the art, there is no special restriction, is preferably argon gas in the present invention.
By Li
2s, P
2s
5with M
2s
nmix in organic solution and react, Li
2s, P
2s
5with M
2s
nformed in organic solution containing Li, P, the compound of M and S, this compound and organic solvent can form crystalline state, organic solvent residual in mixed solution is separated and volatilization in centrifugation and drying course, simultaneously most of crystalline state solvent also can separated and volatilization, residual solvent and crystalline state solvent are in volatilization process, nanoaperture is left in solid electrolyte, the existence of nanoaperture not only increases the specific area of sulfide solid electrolyte material, make sulfide solid electrolyte material particle comparatively fine and smooth simultaneously, be easy to compacting densification, thus increase its ionic conductivity.From said process, sulfide solid electrolyte material preparation process of the present invention is simple, only needs Li
2s, P
2s
5with M
2s
nbe mixed in organic solution, then through stirring-reaction, centrifugal, filter and heat treatment, can sulfide solid electrolyte material be obtained, and at room temperature can complete the preparation of sulfide electrolyte material.When containing double bond organic group in organic solvent, this double bond is easy to Li
+in conjunction with the organic compound formed containing Li, in order to keep the electric neutrality of compound, this compounds is also combined with P-S, S-M Compound Phase containing double bond, form the organic compound containing Li, M, P and S, when heat treatment, organic substance in above-mentioned organic compound is thermal decomposited volatilization, and remaining Li, M, P and S four kinds of elements obtain the xLi of different crystalline phase through heat treatments at different
2s
yp
2s
5zM
2s
nsulfide solid electrolyte material.
Experimental result shows, the ionic conductivity under sulfide solid electrolyte material room temperature prepared by the present invention is close to 10
-2scm
-1.Sulfide solid electrolyte material provided by the invention at room temperature has good electricity and chemical property, can meet the requirement of use.
In order to understand the present invention further, be described in detail to sulfide solid electrolyte material provided by the invention and preparation method thereof below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Under argon gas atmosphere protection and under room temperature, purity is respectively the Li of more than 99%
2s, P
2s
5with GeS
2after weighing according to mol ratio 5:1:1, load be less than the condition of 100ppm in water content under in reaction vessel, then add acetonitrile (AN) according to 300% mass ratio.AN need first adopt Rotary Evaporators repeatedly to distill, and makes its water content be less than 1%.Mix acquisition first just material after adding AN, after expecting at room temperature magnetic agitation 24h at the beginning of first, obtain the suspension-turbid liquid with white precipitate, be the second first material; By the second just material immigration centrifuge tube, centrifugation 10min under 10000rpm rotating speed, then normal temperature filters washing, repeats this step 3 time and obtains the 4th first material; Just expect the 4th to put into baking oven, dry 10h for 100 DEG C and obtain white solid, namely the 5th just expects; Just expect the 5th to put into sintering mold, after 670 DEG C of heat treatment 1h, namely obtain 72%Li
2s14%P
2s
514%GeS
2sulfide solid electrolyte material, its preparation flow figure as shown in Figure 1.
Utilize German D8-Advance (BrukerAXS) X-ray powder diffractometer to the 72%Li obtained in embodiment 1
2s14%P
2s
514%GeS
2sulfide solid electrolyte material carries out material phase analysis, obtains its X ray diffracting spectrum, as shown in Figure 2.Test condition is: radiation source Cu К α, λ=0.15418nm, and sweep limits 2 θ=5 ° ~ 70 °, each sample test time is 20min, and operating voltage is 40kV, and electric current is 40mA.As shown in Figure 2, there is not Li in material
2the crystalline phase diffraction maximum of the raw materials such as S, shows to react completely; The crystalline phase diffraction maximum of material is completely the same compared with standard brick card, and the principal crystalline phase peak of prepared sulfide solid electrolyte material (29.46 ° ± 1 °) peak value is comparatively strong, and half-peak breadth is better, shows that degree of crystallinity is better.
Adopt Hitachi S-4800 field emission scanning electron microscope to the 72%Li obtained in embodiment 1
2s14%P
2s
514%GeS
2sulfide solid electrolyte material carries out morphology analysis, and result as shown in Figure 3.As can be seen from Figure 3, prepared material is porous surface shape, and aperture is about 50nm.
Obtain 72%Li
2s14%P
2s
514%GeS
2after sulfide solid electrolyte material, electrochemical property test is carried out to it.By above-mentioned sulfide solid electrolyte material under water content is less than 100ppm, 10MPa pressure condition, be pressed into that diameter is 10mm, thickness is the sheet 72%Li of 2mm
2s14%P
2s
514%GeS
2sulfide solid electrolyte.Then be blocking electrode with stainless steel, carry out electrochemical impedance spectroscopy (EIS) test at different temperatures, test its electric conductivity, result as shown in figs. 4 and 5.Wherein, Fig. 4 is the AC impedance spectrogram of sulfide solid electrolyte material when room temperature prepared by the embodiment of the present invention 1; Fig. 5 is sulfide solid electrolyte material ionic conductivity curve chart at different temperatures prepared by the embodiment of the present invention 1.As can be seen from Figure 4, the resistance of material is by body phase resistance R
bwith grain boundary resistance R
gtwo parts form, and wherein body phase resistance only 10 ohm, grain boundary resistance is 12 ohm.Fig. 5 can find out, sulfide solid electrolyte material prepared by the present embodiment has macroion conductive characteristic, and under the condition of 25 DEG C, lithium ion conductivity is 7.2 × 10
-3scm
-1, activation energy is 20kJmol
-1.Show the lithium ion conducting characteristic that manufactured sulfide electrolyte material is at room temperature very excellent.
After shaping for above-mentioned all solid lithium secondary battery sulfide electrolyte powder material preforms, respectively with lithium electrode and stainless steel electrode for work electrode, be be assembled into test battery under the condition of 0.1ppm in water content, chronoamperometry test is carried out at 0.2V current potential, to characterize ionic conductivity and the ionic conductance of gained all solid lithium secondary battery sulfide electrolyte material, as shown in Figure 6, Fig. 6 is the chronoamperometry curve chart of sulfide electrolyte material prepared by the embodiment of the present invention 1 to test result; The sulfide electrolyte material that wherein curve a is take lithium electrode as work electrode, prepared by the present embodiment is the chronoa mperometric plot of electrolytical test battery; The sulfide electrolyte material that curve b is take stainless steel as work electrode, prepared by the present embodiment is the chronoa mperometric plot of electrolytical test battery.As shown in Figure 6, the embodiment of the present invention 1 prepare all solid lithium secondary battery sulfide electrolyte material in electronic conductivity be about 1 × 10
-7scm
-1, illustrative material has good ionic conductivity and good electronic isolation, shows that the electrochemical stability of all solid lithium secondary battery sulfide electrolyte material that the present embodiment 1 provides is better, is suitable for being applied to solid lithium battery.
Above-mentioned all solid lithium secondary battery sulfide electrolyte powder body material is loaded wall thickness to be less than in the capillary glass tube of 1 micron, then adopts alcohol blast burner or oxyhydrogen flame by capillary glass tube hot melt tube sealing.Above-mentioned all solid lithium secondary battery sulfide solid electrolyte will be housed and capillary glass tube after tube sealing carries out Raman test, to characterize the structure of prepared sulfide solid electrolyte, as shown in Figure 7, Fig. 7 is the Raman spectrogram of sulfide electrolyte material prepared by the embodiment of the present invention 1, wherein, 421cm
-1displacement place is for being (PS
4)
3-the spectrum peak of fast lithium ion conducting group, 382cm
-1displacement place is not containing the (GeS of bridge joint sulphur
0.5s
3)
3-the spectrum peak of group, 364cm
-1displacement place is Li
+-S
-the spectrum peak of stretching vibration key, 277cm
-1displacement place is (GeS
0.5)
4the spectrum peak of group.
Adopt cobalt acid lithium to be positive pole, Li-In alloy is negative pole, is assembled into all solid lithium secondary battery together with above-mentioned all solid lithium secondary battery sulfide electrolyte material.Carry out charge-discharge test to all solid lithium secondary battery, test result is shown in Fig. 8.As shown in Figure 8, all solid lithium secondary battery sulfide solid electrolyte obtained and the compatibility of oxide electrode material better.
Embodiment 2
Under argon gas atmosphere protection and room temperature, purity is respectively the Li of more than 99%
2s, P
2s
5with GeS
2after weighing according to mol ratio 5:1:1, load be less than the condition of 100ppm in water content under in reaction vessel, then add oxolane (THF) according to 300% mass ratio.THF need first adopt Rotary Evaporators repeatedly to distill, and makes its water content be less than 1%.Obtain first after adding THF solution just to expect, obtain the suspension-turbid liquid with white precipitate after just material room temperature lower magnetic force stirs 24h to first, be second and just expect; By in the second just material immigration centrifuge tube, centrifugation 10min under 10000rpm rotating speed, then normal temperature filters washing, repeats this step 3 time and obtains the 4th first material; Just expect the 4th to put into baking oven, dry 10h in 120 DEG C and obtain white solid, namely the 5th just expects; Just expect the 5th to put into sintering mold, namely 500 DEG C of heat treatment 1h obtain 72%Li
2s14%P
2s
514%GeS
2sulfide solid electrolyte material.
The chemical property of the sulfide electrolyte material that the present embodiment obtains is tested according to the method for embodiment 1.Result shows, and under the condition of 25 DEG C, its lithium ion conductivity is 6.02 × 10
-3scm
-1.Show that the sulfide electrolyte material conductivity at room temperature that the present embodiment provides is better.
Embodiment 3
Under argon gas atmosphere protection and room temperature, purity is respectively the Li of more than 99%
2s, P
2s
5with GeS
2after weighing according to mol ratio 13:2:3, load be less than the condition of 100ppm in water content under in reaction vessel, then add acetonitrile solution according to 300% mass ratio.Acetonitrile need first adopt Rotary Evaporators repeatedly to distill, and makes its water content be less than 1%.Obtain first after adding acetonitrile solution just to expect, obtain the suspension-turbid liquid with white precipitate after just material room temperature lower magnetic force stirs 24h to first, be second and just expect; By in the second just material immigration centrifuge tube, centrifugation 10min under 10000rpm rotating speed, then normal temperature filters washing, repeats this step 3 time and obtains the 4th first material; Just expect the 4th to put into baking oven, dry 10h in 100 DEG C and obtain white solid, namely the 5th just expects; Just expect the 5th to put into sintering mold, namely 600 DEG C of heat treatment 1h obtain 72%Li
2s11%P
2s
517%GeS
2sulfide solid electrolyte material.
The chemical property of the sulfide electrolyte material that the present embodiment obtains is tested according to the method for embodiment 1.Result shows, and under the condition of 25 DEG C, its lithium ion conductivity is 5.02 × 10
-3scm
-1.Show that the sulfide electrolyte material conductivity at room temperature that the present embodiment provides is better.
Embodiment 4
Under argon gas atmosphere protection and room temperature, purity is respectively the Li of more than 99%
2s, P
2s
5with GeS
2after weighing according to mol ratio 13:2:3, load be less than the condition of 100ppm in water content under in reaction vessel, then add oxolane according to 300% mass ratio.Oxolane need first adopt Rotary Evaporators repeatedly to distill, and makes its water content be less than 1%.Obtain first after adding oxolane just to expect, obtain the suspension-turbid liquid with white precipitate after just material room temperature lower magnetic force stirs 24h to first, be second and just expect; By in the second just material immigration centrifuge tube, centrifugation 10min under 10000rpm rotating speed, then normal temperature filters washing, repeats this step 3 time and obtains the 4th first material; Just expect the 4th to put into baking oven, dry 10h in 100 DEG C and obtain white solid, namely the 5th just expects; Just expect the 5th to put into sintering mold, namely 550 DEG C of heat treatment 1h obtain 72%Li
2s11%P
2s
517%GeS
2sulfide solid electrolyte material.
The chemical property of the sulfide electrolyte material that the present embodiment obtains is tested according to the method for embodiment 1.Result shows, and under the condition of 25 DEG C, its lithium ion conductivity is 4.75 × 10
-3scm
-1.Show that the sulfide electrolyte material conductivity at room temperature that the present embodiment provides is better.
Embodiment 5
Under argon gas atmosphere protection and room temperature, purity is respectively the Li of more than 99%
2s, P
2s
5, GeS
2with Al
2s
3after weighing according to mol ratio 5:1:0.95:0.05, load be less than the condition of 100ppm in water content under in reaction vessel, then add acetonitrile according to 300% mass ratio.Acetonitrile need first adopt Rotary Evaporators repeatedly to distill, and makes its water content be less than 1%.Obtain first after adding acetonitrile just to expect, obtain the suspension-turbid liquid with white precipitate after just material room temperature lower magnetic force stirs 24h to first, be second and just expect; By in the second just material immigration centrifuge tube, centrifugation 10min under 10000rpm rotating speed, then normal temperature filters washing, repeats this step 3 time and obtains the 4th first material; Just expect the 4th to put into baking oven, dry 10h in 100 DEG C and obtain white solid, namely the 5th just expects; Just expect the 5th to put into sintering mold, namely 670 DEG C of heat treatment 1h obtain 72%Li
2s14%P
2s
513.3%GeS
20.7%Al
2s
3sulfide solid electrolyte material.
The chemical property of the sulfide electrolyte material that the present embodiment obtains is tested according to the method for embodiment 1.Result shows, and under the condition of 25 DEG C, its lithium ion conductivity is 5.02 × 10
-3scm
-1.Show that the sulfide electrolyte material conductivity at room temperature that the present embodiment provides is better.
Embodiment 6
Under argon gas atmosphere protection and room temperature, purity is respectively the Li of more than 99%
2s, P
2s
5, GeS
2with Al
2s
3after weighing according to mol ratio 5:1:0.95:0.05, load be less than the condition of 100ppm in water content under in reaction vessel, then add oxolane according to 300% mass ratio.Oxolane need first adopt Rotary Evaporators repeatedly to distill, and makes its water content be less than 1%.Obtain first after adding oxolane just to expect, obtain the suspension-turbid liquid with white precipitate after just material room temperature lower magnetic force stirs 24h to first, be second and just expect; By in the second just material immigration centrifuge tube, centrifugation 10min under 10000rpm rotating speed, then normal temperature filters washing, repeats this step 3 time and obtains the 4th first material; Just expect the 4th to put into baking oven, dry 10h in 100 DEG C and obtain white solid, namely the 5th just expects; Just expect the 5th to put into sintering mold, namely 550 DEG C of heat treatment 1h obtain 72%Li
2s14%P
2s
513.3%GeS
20.7%Al
2s
3sulfide solid electrolyte material.
The chemical property of the sulfide electrolyte material that the present embodiment obtains is tested according to the method for embodiment 1.Result shows, and under the condition of 25 DEG C, its lithium ion conductivity is 5.42 × 10
-3scm
-1.Show that the sulfide electrolyte material conductivity at room temperature that the present embodiment provides is better.
Embodiment 7
Under argon gas atmosphere protection and room temperature, purity is respectively the Li of more than 99%
2s, P
2s
5, GeS
2with TiS
2after weighing according to mol ratio 5:1:0.95:0.05, load be less than the condition of 100ppm in water content under in reaction vessel, then add acetonitrile according to 300% mass ratio.Acetonitrile need first adopt Rotary Evaporators repeatedly to distill, and makes its water content be less than 1%.Obtain first after adding acetonitrile just to expect, obtain the suspension-turbid liquid with white precipitate after just material room temperature lower magnetic force stirs 24h to first, be second and just expect; By in the second just material immigration centrifuge tube, centrifugation 10min under 10000rpm rotating speed, then normal temperature filters washing, repeats this step 3 time and obtains the 4th first material; Just expect the 4th to put into baking oven, dry 10h in 100 DEG C and obtain white solid, namely the 5th just expects; Just expect the 5th to put into sintering mold, namely 700 DEG C of heat treatment 1h obtain 72%Li
2s14%P
2s
513.3%GeS
20.7%TiS
2sulfide solid electrolyte material.
The chemical property of the sulfide electrolyte material that the present embodiment obtains is tested according to the method for embodiment 1.Result shows, and under the condition of 25 DEG C, its lithium ion conductivity is 5.17 × 10
-3scm
-1.Show that the sulfide electrolyte material conductivity at room temperature that the present embodiment provides is better.
Embodiment 8
Under argon gas atmosphere protection and room temperature, purity is respectively the Li of more than 99%
2s, P
2s
5, GeS
2with TiS
2after weighing according to mol ratio 5:1:0.95:0.05, load be less than the condition of 100ppm in water content under in reaction vessel, then add oxolane according to 300% mass ratio.Oxolane need first adopt Rotary Evaporators repeatedly to distill, and makes its water content be less than 1%.Obtain first after adding oxolane just to expect, obtain the suspension-turbid liquid with white precipitate after just material room temperature lower magnetic force stirs 24h to first, be second and just expect; By in the second just material immigration centrifuge tube, centrifugation 10min under 10000rpm rotating speed, then normal temperature filters washing, repeats this step 3 time and obtains the 4th first material; Just expect the 4th to put into baking oven, dry 10h in 100 DEG C and obtain white solid, namely the 5th just expects; Just expect the 5th to put into sintering mold, namely 600 DEG C of heat treatment 1h obtain 72%Li
2s14%P
2s
513.3%GeS
20.7%TiS
2sulfide solid electrolyte material.
The chemical property of the sulfide electrolyte material that the present embodiment obtains is tested according to the method for embodiment 1.Result shows, and under the condition of 25 DEG C, its lithium ion conductivity is 5.21 × 10
-3scm
-1.Show that the sulfide electrolyte material conductivity at room temperature that the present embodiment provides is better.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection range of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. the sulfide solid electrolyte material shown in a formula (I):
xLi
2S·yP
2S
5·zM
2S
n(I)；
Wherein, x+y+z=100%; M is one or more in Al, Ge, Ti and La; N is the chemical valence of M.
2. sulfide solid electrolyte material according to claim 1, is characterized in that, the span of described x is 40% ~ 80%.
3. a preparation method for sulfide solid electrolyte material, is characterized in that, comprises the following steps:
A) by Li
2s, P
2s
5, M
2s
nmix with organic solvent, obtain suspension; Li
2s, P
2s
5with M
2s
nmol ratio be x:y:z;
B) by described mixed solution successively through stirring-reaction, centrifugal, filter with drying after, obtain at the beginning of expect;
C) described just material is heat-treated, obtain the sulfide solid electrolyte material shown in formula (I);
xLi
2S·yP
2S
5·zM
2S
n(I)；
Wherein, x+y+z=100%; M is one or more in Al, Ge, Ti and La; N is the chemical valence of M.
4. preparation method according to claim 3, is characterized in that, described organic solvent be selected from alcohols solvent, ether solvent and nitrile solvents one or more.
5. preparation method according to claim 4, is characterized in that, described organic solvent be selected from ethanol, propyl alcohol, penta hexanol, ether, acetonitrile and oxolane one or more.
6. preparation method according to claim 3, is characterized in that, the water content of described organic solution is less than 1wt%.
7. preparation method according to claim 3, is characterized in that, the speed of described stirring is 30rpm ~ 800rpm, and the time of described stirring is 10h ~ 80h; Described centrifugal rotating speed is 3000rpm ~ 20000rpm, and the described centrifugal time is 0 ~ 60min; The time of described drying is 0 ~ 20h, and the temperature of described drying is 60 DEG C ~ 200 DEG C.
8. preparation method according to claim 3, is characterized in that, described heat treated temperature is 200 DEG C ~ 700 DEG C, and the described heat treated time is 0.5h ~ 10h.
9. preparation method according to claim 3, is characterized in that, described mixing, stirring-reaction, centrifugal, filter, dry and heat treatment carries out all be less than the environment of 10% in humidity under.
10. preparation method according to claim 3, is characterized in that, described mixing, stirring-reaction, centrifugal, filter, dry and heat treatment carries out independently of one another under the condition of closed environment or inert gas shielding.
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