CN110137565A - A kind of large-scale producing method of sulfide solid electrolyte - Google Patents
A kind of large-scale producing method of sulfide solid electrolyte Download PDFInfo
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- CN110137565A CN110137565A CN201910419366.5A CN201910419366A CN110137565A CN 110137565 A CN110137565 A CN 110137565A CN 201910419366 A CN201910419366 A CN 201910419366A CN 110137565 A CN110137565 A CN 110137565A
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- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
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Abstract
The present invention provides a kind of large-scale producing method of sulfide solid electrolyte, include the following steps: that (1) carries out vacuum drying to the source Li, the source Si, the source P, the source S, the source Cl raw material；(2) cryogenic vacuum pre-burning is carried out to the raw material after drying；(3) raw material after pre-burning are crushed, control the particle diameter distribution of raw material；(4) screening process is carried out to broken rear raw material, controls partial size；(5) iron removal by magnetic separation is carried out to the raw material after screening；(6) source Li after iron removal by magnetic separation, the source Si, the source P, the source S, the source Cl raw material are successively added portionwise in reaction vessel, charging tray is in stirring during feeding intake；(7) raw material after addition reaction vessel are premixed；(8) raw material after premix are ground.The large-scale producing method precision of sulfide solid electrolyte of the present invention is high, safety is good, loss is small, environmental protection and energy saving, can carry out industrialization preparation.
Description
Technical field
The invention belongs to solid electrolyte fields, more particularly, to a kind of large scale preparation side of sulfide solid electrolyte
Method.
Background technique
Prepare that sulfide solid electrolyte in-process inventory is more in industrialization, and the quality of raw material is different, exists
Certain agglomeration, and mixed process is continuous, flowing, the material proportion of local mixing and former stoichiometric ratio exist compared with
Big difference, and be affected by raw material feeding sequence and quantity, therefore laboratory desired effect is often not achieved, it causes
Raw material mixing is uneven, influences the quality and yield of product.
Using the equipment such as sand mill, airflow milling in preparation process, production efficiency is improved using continuously grinding, and inventory compared with
Greatly, laboratory expected effect is not achieved in grinding effect, causes material to be unable to get and is fully ground, and especially material mixes not
After uniformly, do not improved during the grinding process, the component ratio of product may not be design proportion, and structure also will appear
Ingredient in relatively large deviation, especially " shell ".
Summary of the invention
In view of this, the present invention is directed to propose a kind of large-scale producing method of sulfide solid electrolyte, can carry out big
Large-scale production.
In order to achieve the above objectives, the technical scheme of the present invention is realized as follows:
A kind of large-scale producing method of sulfide solid electrolyte, includes the following steps:
(1) vacuum drying is carried out to the source Li, the source Si, the source P, the source S, the source Cl raw material；
(2) cryogenic vacuum pre-burning is carried out to the raw material after drying；
(3) raw material after pre-burning are crushed, control the particle diameter distribution of raw material；
(4) screening process is carried out to broken rear raw material, controls partial size；
(5) iron removal by magnetic separation is carried out to the raw material after screening；
(6) source Li after iron removal by magnetic separation, the source Si, the source P, the source S, the source Cl raw material are successively added portionwise in reaction vessel,
Charging tray is in stirring during feeding intake；
(7) raw material after addition reaction vessel are premixed；
(8) raw material after premix are ground；
(9) material after grinding is sintered under an inert atmosphere, sulfide solid state electrolysis is obtained after the completion of sintering
Matter.
Further, the elemental mole ratios of the raw material are Li:Si:P:S:Cl=(7-12): (0-2): (0-2):
(10-12):(0-1)；The source Li is Li2S、LiCl、Li2CO3, LiOH, at least one of lithium acetate or lithium metal；Institute
The source Si stated is SiS2、SiO2, at least one of SiC or S；The source P is P2S5, red phosphorus, yellow phosphorus, P2O5Or in phosphoric acid
It is at least one；The source S is Li2S、P2S5、SiS2Or at least one of S；The source Cl be LiCl, liquid chlorine, chloroform or
At least one of chlorinated organics；The raw material are LiCl, Li2S、P2S5、SiS2；Described step (6) chinese raw materials
Feeding sequence successively are as follows: LiCl, Li2S、P2S5、SiS2、LiCl。
Further, temperature is 105-120 DEG C in vacuum drying step in the step (1), vacuum degree 133Pa-
1KPa, baking time 3-10h.Vacuum drying step can reduce the moisture in material and the content of adsorbed gas.
Further, the temperature of low temperature presintering step is 150-200 DEG C in the step (2), burn-in time 1-5h；Institute
It is 500nm-1um that the partial size of raw material, which is D10, after the completion of destruction step in the step of stating (3), and D50 1um-5um, D90 are
5um-10um；It is 500nm-700nm that the partial size of raw material, which is D10, after the completion of screening step in the step (4), and D50 is
1um-3um, D90 5um-7um.Low temperature presintering is carried out to material, reduces the organic remains of material surface absorption.
The screening plant of screening step uses vibrating screen, 2000 times/min of vibration frequency in step (4), and oscillating region is
0.5-12mm, inclination angle is in 10-30 degree.
Further, the magnetism intensity of iron removal by magnetic separation step is 10000-15000Gs, processing speed in the step (5)
For 650-700 Kg/h, iron removal by magnetic separation step is repeated 1-2 times.Iron removal by magnetic separation can reduce containing for the impurity F e that reaction vessels are brought into
Amount.
It by control feeding sequence in step (6), and is fed intake using repeatedly circulation, ingredients can be improved, avoid
Transfer vessel (including mixing vessel) is excessive to certain single material adhesive capacity, and material is caused to lose because of ratio caused by adhesion loss
Weighing apparatus, and covering sulfur-containing compound sufficiently by LiCl, reduction and air contact surfaces reduce rotten risk, improve raw material
Proportion precision, it is ensured that raw material by setting stoichiometric ratio matched.
The particle size range of material in the step (7) after the completion of pre-mixing process: D10 500nm-1um, D50 are
1um-5um, D90 5um-10um.The homogeneous grain diameter of material in mixing process is controlled, raw material agglomeration traits are reduced.A variety of materials
The mobility and adhesiveness of material have differences, and under the high speed rotation of batch mixer, easily adhere on impeller and casing wall, in order to true
Protecting the proportion of raw material entered in high speed mixer is ingredient proportion, is premixed to the raw material prepared.
The batch mixer of pre-mixing process uses vertical mixer in step (7), and incorporation time exists in 5-10min, simple mixing
500-1000L.Vertical mixer mixing efficiency is high, effect is good, has and shortens the production cycle, improves the effect of subsequent grinding.
Further, the ratio of grinding media to material of grinding steps is 2-5:1, linear velocity 9-15m/s, filling rate in the step (8)
For 70-85%, ball milling pearl is having a size of 1-10mm, circular grinding；In the step (8) after the completion of grinding steps material partial size
Range are as follows: 500nm-700nm, D50 1um-3um, D90 5um-7um.Ratio of grinding media to material and grinding frequency are improved, grinding effect is improved
Can, using circular grinding, processes such as grinding step by step, grinding efficiency and effect are improved, concrete operations are that the material of discharge port is collected
Afterwards, further grinding, improves ratio of grinding media to material, improves lap speed, realizes that the refinement again to material mixes.
Further, in the step (8) the step of process of lapping are as follows: then first positive grinding 20min-1h is reversely ground
20min-1h is ground, turning to interval time control is 2-5min, integral grinding duration 30-50h, and passes through water cooling, circulating water temperature
It is 7-15 DEG C, recirculated water flow velocity is 80-100m3/ h, grinding cavit temperature are 20-50 DEG C, and powder surface temperature is less than or equal to 150
℃。
Further, the calcined temperature of sintering step is 120-200 DEG C in the step (9), sintering temperature 400-700
DEG C, when sintering a length of 8-10h, heating rate is 5-10 DEG C/min, and holding temperature is 100-150 DEG C, is then cooled to room temperature.
Further, sintering step carries out the pre-heat treatment, intake air temperature control to the air inlet of inert gas in the step (9)
It is made as 200-250 DEG C；The inert gas is Ar or N2。
Further, the material fltting speed of sintering step is 0.8-1.5m/h in the step (9)；The step
(9) temperature control precision of sintering step ensures that fluctuation is less than 0.5 DEG C in every 1m in；Sintering step in the step (9)
The every 0.5h of material carries out once vibrating to stir shaking up.Ensure that material firing is fired in reasonable temperature range.
Every 0.5h turning over materials can also be used vibration and mix, and using the notched saggar in four sides, guarantee the material in saggar
Temperature is consistent, and the working sections temperature difference is less than 3 DEG C.Burning process route, firing time are controlled by computer, overturning mixes number
With annealing process, it is ensured that be precisely controlled.
Further, sulfide solid electrolyte made from the step (9) is solid for A-M-B-C (- X) type crystal sulfide
One of state electrolyte, wherein A is at least one of Li, Na, Mg or Al；M is at least one of Si, Ge or Sn；B is
At least one of P or Sb；C is at least one of O, S or Se；X is at least one of F, Cl, Br or I.
Compared with the existing technology, the large-scale producing method of sulfide solid electrolyte of the present invention has following excellent
Gesture:
The large-scale producing method of sulfide solid electrolyte of the present invention is obtained using mechanical lapping and high-temperature process
To sulfide solid electrolyte, each step precision is high, safety is good, loss is small, environmental protection and energy saving, can carry out industrialization preparation.
Detailed description of the invention
Fig. 1 is the STEM shape appearance figure of product in the embodiment of the present invention 1；
Fig. 2 is the EDS result of the Si of product in the embodiment of the present invention 1；
Fig. 3 is the EDS result of the P of product in the embodiment of the present invention 1；
Fig. 4 is the EDS result of the S of product in the embodiment of the present invention 1；
Fig. 5 is the diffracting spectrum that calculated characterization monocrystalline LSPS is simulated in the embodiment of the present invention 1；
Fig. 6 is the diffracting spectrum of product in the embodiment of the present invention 1；
Fig. 7 is the CV test result of product in the embodiment of the present invention 1.
Specific embodiment
In addition to being defined, technical term used in following embodiment has universal with those skilled in the art of the invention
The identical meanings of understanding.Test reagent used in following embodiment is unless otherwise specified conventional biochemical reagent；It is described
Experimental method is unless otherwise specified conventional method.
Below with reference to embodiment, the present invention will be described in detail.
Embodiment 1
A kind of large-scale producing method of sulfide solid electrolyte, includes the following steps:
(1) to LiCl, Li2S、P2S5、SiS2(vacuum baking is carried out for 2.3:38.9:29.3:29.4) raw material in mass ratio
Dry, temperature is 120 DEG C, vacuum degree 133Pa, baking time 5h, then utilizes moisture tester (Switzerland ten thousand is logical) test material
Moisture in material；
(2) low temperature presintering is carried out to the raw material after drying, reduces the organic remains of material surface absorption, calcined temperature
It is 150 DEG C, burn-in time 3h；
(3) raw material after pre-burning are crushed, using kibbler roll comminution of material, (500mm roller is wide, diameter
800mm), the particle diameter distribution (D10 500nm-1um, D50 1um-5um, D90 5um-10um) of raw material is controlled；
(4) screening process is carried out to broken rear raw material, controls partial size, (D10 500nm-700nm, D50 1um-
3um, D90 5um-7um), screening plant uses vibrating screen, and vibration frequency 2000 times/min, oscillating region 0.5-12mm incline
Oblique angle is in 10-30 degree；
(5) iron removal by magnetic separation is carried out to the raw material after screening, reduces the content for the impurity F e that reaction vessels are brought into, magnetic force is strong
Degree is 12000Gs, and processing speed is 650-700 Kg/h；
(6) by LiCl, Li after iron removal by magnetic separation2S、P2S5、SiS2, LiCl (be in mass ratio 1.0:38.9:29.3:
29.4:1.3) raw material are successively added portionwise in reaction chamber, and charging tray is in stirring during feeding intake, and control feeding sequence,
And fed intake using repeatedly circulation, ingredients can be improved, transfer vessel, mixing vessel is avoided to adhere to certain single material
Measure excessive, cause material because of proportional imbalance caused by adhesion loss, and covering sulfur-containing compound sufficiently by LiCl, reduce with
Air contact surfaces reduce rotten risk, improve the proportion precision of raw material, it is ensured that raw material by setting stoichiometric ratio into
Row proportion, weighs and selects high-precision weighing sensor, improves the precision (brand: Transcell) of weighing process；
(7) raw material after addition reaction vessel are premixed, controls the homogeneous grain diameter (D10 of material in mixing process
About 600nm, D50 are about 3um, and D90 is about 7um), the problem of raw material are reunited is reduced, batch mixer uses vertical mixer, mixes
The time is closed in 5min, simple mixing carries out sampling observation analysis in 500L；
(8) it carries out grinding to the raw material after premix to mix, ratio of grinding media to material 3:1, linear velocity 12m/s, filling rate
It is 80%, collection material after the completion, the particle size range of material after the completion of grinding are as follows: D10 is about 150nm, and D50 is about 1um, D90
It is about 2um；
(9) material after grinding is sintered under Ar protection, is arranged using three layers of saggar of biserial, front-end temperature is about
200 DEG C, middle section temperature is about 470 DEG C, and endpiece temperature is about 150 DEG C, and materials vehicle stepping rate is about 1.2m/h, and when sintering is a length of
8h, heating rate carry out the pre-heat treatment to air inlet about in 5 DEG C/min, avoid influencing the Temperature Distribution in kiln, intake air temperature control
At 250 DEG C, using baroceptor and automatic flow meter, realize that air inflow and kiln inner pressure keep dynamic equilibrium, following in kiln
Ring gas needs to be evenly distributed in kiln road, especially ensures that temperature cycles in multilayer saggar, selects High Accuracy Thermocouple Temperature (nickel chromium triangle
CopperNickel thermocouple, local precise temperature control use platinum rhodium thermocouple), reasonable arrangement thermocouple distributed area improves the temperature to kiln
Degree control, temperature control precision ensure that fluctuation is less than 0.5 DEG C in every 1m, it is ensured that material firing is burnt in reasonable temperature range
System, every 0.5h turning over materials are mixed using vibration, using the notched saggar in four sides, guarantee that the temperature of charge in saggar is consistent,
The working sections temperature difference less than 3 DEG C, by computer control burning process route, the firing time, overturning mix number with it is annealed
Journey, it is ensured that be precisely controlled, LGPS type crystal sulfide solid electrolyte is obtained after the completion of sintering
(Li9.54Si1.74P1.44S11.7Cl0.3)。
The step of process of lapping are as follows: then first positive grinding 1h reversely grinds 1h, turning to interval time control is 5-
10min, and by water cooling, circulating water temperature is 12 DEG C, and recirculated water flow velocity is 80m3/ h, grinding cavit temperature are 30 DEG C, powder
Surface temperature is no more than 150 DEG C.
Material transfer process uses encapsulation process (thick 0.5mm aluminum plastic film vacuum seal), delivers and uses in blending process
Material pumping pipeline avoids repeatedly shifting bring raw material losses and pollution, pipeline is using more using pipeline transportation raw material
Layer composite construction, outer layer is stainless steel, internal layer is antifriction scrape along smooth layer, and material is Teflon or polyurethane.
Material transfer uses abrasion-proof stainless steel pipeline, avoids contacting with air, and transport atmosphere uses inert atmosphere
(Ar/N2), it is matched using automatic weighting, improves production efficiency, prevented material and air reaction and go bad.In sintering process into
Gas outlet is specially recycled using pipeline, concentrates purified treatment (dedirt, dehydration, absorption H2S etc.), it utilizes again, improves protection gas
Body utilization rate.It can use tail gas heat quantity simultaneously to heat air inlet, be conducive to the temperature control in material sintering procedure
System.Building of production line place needs humid control, and -40 DEG C of general control dew point avoids moisture from bringing the side reaction to material,
And generate toxic and harmful gas.
Using high-accuracy sensor, (weighing sensor, displacement sensor, pressure sensor, temperature sensor, gas are passed
Sensor, water-oxygen sensor etc.), it is monitored to raw material automatic weighting, with when mixed effect, to temperature in process of lapping
And ratio of grinding media to material is monitored in real time, periodically inspects mixing material, laser particle size analyzer and desktop SEM by random samples, quickly analysis grinding is imitated
Fruit (size distribution and surface topography), is monitored in real time (especially water partial pressure and oxygen to the atmosphere in transfer conduit and kiln
Partial pressure), in kiln temperature and gas content be monitored, rate of the adjust automatically material into kiln, it is ensured that all reactions are pressed
Design requirement carries out.
The LGPS type crystal sulfide solid electrolyte being prepared in embodiment 1
(Li9.54Si1.74P1.44S11.7Cl0.3), using a variety of detection methods to its pattern, ingredient, partial size, crystal structure, electrochemistry
It can be carried out accurate characterization, result is as follows:
It is produced 1. being obtained using scanning transmission electron microscope technology (STEM) and energy dispersive X-ray spectral technique (EDS)
The information of the patterns of product, ingredient, partial size.Sample reduces or prevents interference of the air to sample in transfer process.Concrete outcome is such as
Shown in Fig. 1-4.Would know that material is broadly divided into two parts from the STEM result in Fig. 1, center is " core " structure of sample,
External uniformly one layer of thin layer " shell " structure of package, and the smooth thickness of " shell " shape radian is uniform, is formed good spherical.From 2-4
The ingredient of sample " core " and " shell " is Si, P, S (Li can not be detected by EDS, not shown), but shell phase pair known to the EDS figure of figure
In electron beam traffic direction thickness very little for core, the X-ray signal of generation is far weaker than core, therefore EDS weak output signal.EDS
As a result consistent with experimental design material component.In addition, the partial size of " core " is in 6um or so, shell with a thickness of 1.5um or so, LSPS
Integral particle partial size is in 9um or so.
2. obtaining the crystal structure information of sample using X-ray diffractometer (XRD).Test major parameter: Cu target, scanning step
0.02 ° long, scanning range is 10-70 °, and concrete outcome is as seen in figs. 5-6.It is composed from the standard diffraction peak of software simulation LSPS and real
The diffraction maximum spectrum comparative analysis of product is tested, all peak positions of the two can correspond to, and belong to space group P42/ nmc, 137, indicate real
The crystal structure and LSPS mono-crystalline structures for testing product fit like a glove.In conjunction with the experiment analysis results of STEM-EDS, it can determine that and closed
It is LSPS at product, and major part is crystalline state.After carrying out refine Fitting Analysis to the XRD diffraction maximum of product, its lattice is obtained
Lattice parameter in parameter a=8.7008667, c=12.6071594, with software simulation LSPS normal structure is completely the same, can
Know that synthesized product is pure LSPS, it is consistent with experimental design.
3. obtaining the electrochemical stability information of sample using cyclic voltammetry (CV).Test major parameter: voltage range
2.5-4.0V, sweep speed 0.1mV/s, electrochemical cell system is Li/Glassfiber/LSPS-Cl+C/Au, specific to tie
Fruit is as shown in Figure 7.It is found that the product synthesized by 1 the method for embodiment, initial oxidation decomposition voltage are mentioned from result
Height has arrived about 3.09V, much larger than current universally recognized LSPS material initial oxidation decomposition voltage (2.1V).And 3-5V's
The oxygenolysis current density of the product is smaller in high voltage range, can deduce that its high voltage withstanding performance is more excellent.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of large-scale producing method of sulfide solid electrolyte, characterized by the following steps:
(1) vacuum drying is carried out to the source Li, the source Si, the source P, the source S, the source Cl raw material；
(2) cryogenic vacuum pre-burning is carried out to the raw material after drying；
(3) raw material after pre-burning are crushed, control the particle diameter distribution of raw material；
(4) screening process is carried out to broken rear raw material, controls partial size；
(5) iron removal by magnetic separation is carried out to the raw material after screening；
(6) source Li after iron removal by magnetic separation, the source Si, the source P, the source S, the source Cl raw material are successively added portionwise in reaction vessel, are fed intake
Charging tray is in stirring in the process；
(7) raw material after addition reaction vessel are premixed；
(8) raw material after premix are ground；
(9) material after grinding is sintered under an inert atmosphere, sulfide solid electrolyte is obtained after the completion of sintering.
2. the large-scale producing method of sulfide solid electrolyte according to claim 1, it is characterised in that: the original
The elemental mole ratios of material are Li:Si:P:S:Cl=(7-12): (0-2): (0-2): (10-12): (0-1)；The source Li is
Li2S、LiCl、Li2CO3, LiOH, at least one of lithium acetate or lithium metal；The source Si is SiS2、SiO2, in SiC or S
At least one；The source P is P2S5, red phosphorus, yellow phosphorus, P2O5Or at least one of phosphoric acid；The source S is Li2S、
P2S5、SiS2Or at least one of S；The source Cl is at least one of LiCl, liquid chlorine, chloroform or chlorinated organics；Institute
The raw material stated are LiCl, Li2S、P2S5、SiS2；The feeding sequence of described step (6) chinese raw materials is successively are as follows: LiCl,
Li2S、P2S5、SiS2、LiCl。
3. the large-scale producing method of sulfide solid electrolyte according to claim 1, it is characterised in that: the step
Suddenly temperature is 105-120 DEG C, vacuum degree 133Pa-1KPa, baking time 3-10h in vacuum drying step in (1)；It is described
The step of (2) in low temperature presintering step temperature be 150-200 DEG C, burn-in time 1-5h；Step is crushed in the step (3)
It is 500nm-1um, D50 1um-5um, D90 5um-10um that the partial size of raw material, which is D10, after the completion of rapid；The step (4)
It is 500nm-700nm, D50 1um-3um, D90 5um-7um that the partial size of raw material, which is D10, after the completion of middle screening step.
4. the large-scale producing method of sulfide solid electrolyte according to claim 1, it is characterised in that: the step
Suddenly the magnetism intensity of iron removal by magnetic separation step is 10000-15000Gs, processing speed 650-700Kg/h, iron removal by magnetic separation step in (5)
It is rapid to repeat 1-2 times；The particle size range of material in the step (7) after the completion of pre-mixing process: D10 500nm-700nm,
D50 is 1um-3um, D90 5um-7um.
5. the large-scale producing method of sulfide solid electrolyte according to claim 1, it is characterised in that: the step
Suddenly the ratio of grinding media to material of grinding steps is 2-5:1 in (8), and linear velocity 9-15m/s, filling rate 70-85%, ball milling pearl is having a size of 1-
10mm, circular grinding；In the step (8) after the completion of grinding steps material particle size range are as follows: D10 50-200nm, D50
For 200nm-1um, D90 1um-2um.
6. the large-scale producing method of sulfide solid electrolyte according to claim 5, it is characterised in that: the step
Suddenly in (8) the step of process of lapping are as follows: then first positive grinding 20min-1h reversely grinds 20min-1h, turns to interval time
Control is 2-5min, integral grinding duration 30-50h, and by water cooling, circulating water temperature is 7-15 DEG C, and recirculated water flow velocity is 80-
100m3/ h, grinding cavit temperature are 20-50 DEG C, and powder surface temperature is less than or equal to 150 DEG C.
7. the large-scale producing method of sulfide solid electrolyte according to claim 1, it is characterised in that: the step
Suddenly the calcined temperature of sintering step is 120-200 DEG C in (9), and sintering temperature is 400-700 DEG C, when sintering a length of 8-10h, heating
Rate is 5-10 DEG C/min, and holding temperature is 100-150 DEG C, is then cooled to room temperature.
8. the large-scale producing method of sulfide solid electrolyte according to claim 1, it is characterised in that: the step
Suddenly sintering step carries out the pre-heat treatment to the air inlet of inert gas in (9), and intake air temperature control is 200-250 DEG C；Described is lazy
Property gas be Ar or N2。
9. the large-scale producing method of sulfide solid electrolyte according to claim 1, it is characterised in that: the step
Suddenly the material fltting speed of sintering step is 0.8-1.5m/h in (9)；The temperature of sintering step controls essence in the step (9)
Degree ensures that fluctuation is less than 0.5 DEG C in every 1m；The every 0.5h of the material of sintering step once vibrate and is stirred in the step (9)
It shakes up.
10. the large-scale producing method of sulfide solid electrolyte according to claim 1, it is characterised in that: described
Sulfide solid electrolyte made from step (9) is one of A-M-B-C (- X) type crystal sulfide solid electrolyte, wherein
A is at least one of Li, Na, Mg or Al；M is at least one of Si, Ge or Sn；B is at least one of P or Sb；C is
O, at least one of S or Se；X is at least one of F, Cl, Br or I.
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| CN117174992A (en) * | 2023-08-14 | 2023-12-05 | 国联汽车动力电池研究院有限责任公司 | Lithium sodium composite inorganic sulfide solid electrolyte material and preparation method thereof |
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| CN110718713A (en) * | 2019-12-02 | 2020-01-21 | 天目湖先进储能技术研究院有限公司 | Large-scale preparation method of halogen-containing crystal sulfide solid electrolyte |
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| CN111943263B (en) * | 2020-08-24 | 2022-11-11 | 中创新航技术研究院(江苏)有限公司 | Solid electrolyte, preparation method thereof and solid battery |
| CN112599848A (en) * | 2020-12-11 | 2021-04-02 | 浙江锋锂新能源科技有限公司 | Batch production method of sulfide solid electrolyte |
| CN117174992A (en) * | 2023-08-14 | 2023-12-05 | 国联汽车动力电池研究院有限责任公司 | Lithium sodium composite inorganic sulfide solid electrolyte material and preparation method thereof |
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