CN110323428A - A kind of anode material of lithium-ion battery and preparation method thereof - Google Patents
A kind of anode material of lithium-ion battery and preparation method thereof Download PDFInfo
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The present invention provides a kind of anode material of lithium-ion batteries and preparation method thereof.The anode material of lithium-ion battery, which is characterized in that including carbon coating hetero-junctions ZnS/SnS nano particle composite material.The present invention forms buffer layer using the space structure of carbon-coating to inhibit the volume expansion of metal sulfide, is to solve anode material of lithium-ion battery metal sulfide poor circulation and the bad effectively simply method of high rate performance.Carbon-coating structure provides the buffer layer for inhibiting its bulk effect for composite nano metal sulfide particle, this is a key factor for improving cycle performance, no carbon-coated metal sulfide negative electrode material is compared, composite material is obviously improved in terms of cycle performance and high rate performance.The resulting carbon coating hetero-junctions ZnS/SnS nano particle composite material of the present invention carries out charge and discharge at 500mA/g, and charging/discharging voltage range is 0-2.5V, capacity about 502mAh/g, has good cyclical stability and capacity retention ratio.
Description
Technical field
The invention belongs to materialogy fields, are related to a kind of negative electrode material of sodium-ion battery, specifically carbon coating is different
The preparation method of matter knot ZnS/SnS nano particle composite material, belongs to sodium-ion battery field.
Background technique
In recent years, sodium-ion battery has been because plurality of advantages has attracted the close attention of domestic and foreign scholars, but and lithium from
Sub- battery is compared, and relevant report is still less.The system completely new as one seeks the novel positive and negative anodes electrode material haveing excellent performance
The exploitation for the electrolyte expected and matched is the key that sodium-ion battery research.Experience based on Study on Li-ion batteries, people
Main research concentrate in sodium-ion battery positive material.Common sodium-ion battery positive material mainly has following several classes:
Cobalt, Mn oxide, phosphoric acid, NASICON structural compounds etc..However the report about negative electrode material is relatively fewer, therefore, having must
It will being furtherd investigate and being studied to negative electrode material.It is well known that the chemical property of sodium-ion battery is mainly by its electricity
What pole material determined, and the positive electrode of sodium-ion battery studies oneself through than wide, and negative electrode material becomes and studies at present
Hot spot.To become the negative electrode material of sodium-ion battery, it is necessary to there are some basic requirements to the performance of material: firstly, the conjunction of sodium
The current potential of aurification process wants low, as close possible to metallic sodium current potential make battery output voltage it is high, and charge and discharge process
Middle voltage is steady.Secondly, specific capacity wants volume expansion in height and charge and discharge process small.Electrode material electronic conductivity and ion-conductance
Conductance is compared with usury in high current charge-discharge.Finally, electrode material must have cheap, rich reserves, environmentally protective no dirt
The advantages that dye.
That is reported at present is several about mainly having for sodium ion negative electrode material: carbon-based material, metal or alloy material
Material, titanate material, organic material, metal sulfide material etc., metal sulfide material is because of its high specific capacity and special
Two-dimensional layered structure and rapidly become the hot spot of research.But metal sulfide material can generate greatly in cyclic process
Volume expansion leads to the dusting of electrode material and falls off, poor so as to cause its cyclical stability.
Summary of the invention
It is an object of the present invention to provide a kind of cyclical stability difference and the preferable anode material of lithium-ion battery of high rate performance and
Preparation method.The present invention is using carbon coating hetero-junctions ZnS/SnS nano particle composite material as sodium-ion battery cathode material
Material, the cladding of carbon-coating can limit metal sulfide bulk effect effectively to reach the mesh for promoting its cyclical stability and high rate performance
, it solves in the prior art since the volume expansion of metal sulfide material causes its cyclical stability difference and high rate performance bad
Deng technical problem.
In order to achieve the above object, the present invention provides a kind of anode material of lithium-ion batteries, which is characterized in that including carbon
Coated dissimilar knot ZnS/SnS nano particle composite material (expression formula is ZnS/SnS@C).
The present invention also provides the preparation methods of above-mentioned anode material of lithium-ion battery, which is characterized in that including as follows
Step:
Step 1: hexahydroxy zinc stannate being added in reaction vessel, ultrasound after deionized water or dehydrated alcohol is added, adds
Enter polyethylene dioxythiophene (PEDOT), glucose or urea, products therefrom is centrifuged, by obtained solid water by magnetic agitation mixing
It washes, it is dry, obtain black powder；
Step 2: by the resulting black powder of step 1 and sulphur powder, thiocarbamide or thioacetamide mixed grinding, obtaining yellow production
Object；
Step 3: the resulting yellow product of step 2 being put into tube furnace, is controlled in hydrogen-argon-mixed or argon atmosphere
Heating rate is that 1-5 DEG C/min is warming up to 400-700 DEG C of heat preservation calcining 3-8h, then cools to room temperature with the furnace, is ground using mortar
It grinds to get carbon coating hetero-junctions ZnS/SnS nano particle composite material is arrived.
Preferably, the calcination temperature is 400 DEG C, 500 DEG C, 600 DEG C or 700 DEG C, soaking time 5h.
Preferably, the milling time in the step 3 is 1.5~2h.
Preferably, the ultrasonic time in the step 1 is 20-40 minutes.
Preferably, the magnetic agitation incorporation time in the step 1 is 3-8 hours.
Preferably, the preparation method of the hexahydroxy zinc stannate includes: to weigh stannic chloride pentahydrate or potassium stannate and hydrogen
Sodium oxide molybdena, which is placed in reaction vessel, is added deionized water, and magnetic agitation obtains solution A, place it in ice water until being completely dissolved
It is stirred 20-40 minutes in bath, weighs white vitriol and be placed in another reaction vessel deionized water is added, magnetic agitation is until complete
Fully dissolved obtains solution B, and solution B is added in solution A, is stirred 10-15 hours in ice-water bath, is centrifuged, by obtained solid water
It washes, it is dry, obtain presoma hexahydroxy zinc stannate.
It is highly preferred that the stannic chloride pentahydrate or potassium stannate, white vitriol, sulphur powder, thiocarbamide or thioacetamide,
And the molar ratio of polyethylene dioxythiophene (PEDOT), glucose or urea is 1:1:2-4.2:0.05-1.67.
The present invention prepares carbon coating hetero-junctions ZnS/SnS nano particle composite material using high temperature solid-state method, prepares first
Polyethylene dioxythiophene (PEDOT) is then used as carbon source to hexahydroxy stannic acid by presoma hexahydroxy zine stannate nano cubic block
Zinc is coated, and is then centrifuged to it, is filtered, resulting solid powder is mixed with sulphur powder, then be placed in and be connected with hydrogen
It is calcined at different temperatures in tube furnace in argon-mixed atmosphere, obtains mentioned carbon coating hetero-junctions ZnS/SnS nanometers above
The compound anode material of lithium-ion battery of grain.
Negative electrode material metal sulfide is supported among carbon-coating by the present invention, since carbon structure is metal sulfide in charge and discharge
Volume expansion in electric process provides cushion space, so that the structure that obtained composite negative pole sodium-ion battery material has had is steady
Qualitative energy, cycle performance and high rate performance are obviously improved relative to the negative electrode material of not carbon-coating, and finally obtaining has
Compared with the sodium-ion battery material of high charge-discharge capacity, excellent cycle performance and high rate performance.The material is compared to no carbon packet
The ZnS/SnS nano particle covered shows better cycle performance and high rate performance.
Compared with prior art, the beneficial effects of the present invention are:
The present invention forms buffer layer using the space structure of carbon-coating to inhibit the volume expansion of metal sulfide, is to solve
Anode material of lithium-ion battery metal sulfide poor circulation and the bad effectively simply method of high rate performance.Carbon-coating knot
Structure provides the buffer layer for inhibiting its bulk effect for composite nano metal sulfide particle, this is one of raising cycle performance important
Factor, compares no carbon-coated metal sulfide negative electrode material, and composite material has in terms of cycle performance and high rate performance
It is obviously improved.The resulting carbon coating hetero-junctions ZnS/SnS nano particle composite material of the present invention carries out charge and discharge at 500mA/g
Electricity, charging/discharging voltage range are 0-2.5V, capacity about 502mAh/g, have good cyclical stability and capacity retention ratio.
Detailed description of the invention
Fig. 1 is the XRD diagram of embodiment 1, embodiment 2, embodiment 3 and the obtained composite material of embodiment 4；
Fig. 2 is the TEM figure of the obtained composite material ZHS500C of embodiment 1；
Fig. 3 is embodiment 1, embodiment 2, embodiment 3, embodiment 4 and the obtained composite material negative electrode material of embodiment 5
Circulation figure at 500mA/g；
Fig. 4 is embodiment 1, embodiment 2, embodiment 3, embodiment 4 and the obtained composite material negative electrode material of embodiment 5
AC impedance figure.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Used each raw material is commercial product in following embodiment.
Embodiment 1
A kind of anode material of lithium-ion battery is carbon coating hetero-junctions ZnS/SnS nano particle composite material.The sodium
Ion battery cathode material the preparation method comprises the following steps:
Step 1: weighing 0.018mol stannic chloride pentahydrate with 0.016mol sodium hydroxide and be placed in a beaker addition 70mL
Ionized water, magnetic agitation obtain solution A, place it in ice-water bath and stir 30 minutes until being completely dissolved, meanwhile, it weighs
0.018mol white vitriol is placed in another beaker, and 10mL deionized water is added, and magnetic agitation obtains molten until being completely dissolved
Solution B is added in solution A, stirs 12 hours in ice-water bath by liquid B, is centrifuged, obtained solid is washed, dry, obtains forerunner
Body hexahydroxy zinc stannate；
Step 2: the resulting hexahydroxy zinc stannate of step 1 being added in beaker, ultrasound 30 after 20mL deionized water is added
Minute, 0.03mol polyethylene dioxythiophene (PEDOT) (analyzing pure, Aladdin reagent Co., Ltd), magnetic agitation mixing is added
5 hours, products therefrom is centrifuged, obtained solid is washed 3 times, it is dry, obtain black powder；By black powder and 0.075mol
Sulphur powder mixed grinding obtains yellow product C, and yellow product C is put into tube furnace, and heating is controlled in hydrogen-argon-mixed atmosphere
Rate is 3 DEG C/min, is warming up to 400 DEG C of heat preservation calcining 5h, then cools to room temperature with the furnace, obtain black powder, use mortar
2h is ground to get carbon coating hetero-junctions ZnS/SnS nano particle composite material (referred to as ZHS400C) is arrived.
Embodiment 2
A kind of anode material of lithium-ion battery is carbon coating hetero-junctions ZnS/SnS nano particle composite material.The sodium
Ion battery cathode material the preparation method comprises the following steps:
Step 1: weighing 0.018mol stannic chloride pentahydrate with 0.016mol sodium hydroxide and be placed in a beaker addition 70mL
Ionized water, magnetic agitation obtain solution A, place it in ice-water bath and stir 30 minutes until being completely dissolved, meanwhile, it weighs
0.018mol white vitriol is placed in another beaker, and 10mL deionized water is added, and magnetic agitation obtains molten until being completely dissolved
Solution B is added in solution A, stirs 12 hours in ice-water bath by liquid B, is centrifuged, obtained solid is washed, dry, obtains forerunner
Body hexahydroxy zinc stannate；
Step 2: the resulting hexahydroxy zinc stannate of step 1 being added in beaker, ultrasound 30 after 20mL deionized water is added
Minute, 0.03mol polyethylene dioxythiophene (PEDOT) (analyzing pure, Aladdin reagent Co., Ltd) is added, magnetic agitation 5 is small
When, products therefrom is centrifuged, obtained solid is washed 3 times, it is dry, obtain black powder；By black powder and 0.075mol sulphur
Powder mixed grinding obtains yellow product C, and yellow product C is put into tube furnace in hydrogen-argon-mixed atmosphere and controls heating rate
500 DEG C of heat preservations are warming up to for 3 DEG C/min and calcine 5h, are then cooled to room temperature with the furnace, are obtained black powder, use mortar grinder
2h to get arrive carbon coating hetero-junctions ZnS/SnS nano particle composite material (referred to as ZHS500C).
Embodiment 3
A kind of anode material of lithium-ion battery is carbon coating hetero-junctions ZnS/SnS nano particle composite material.The sodium
Ion battery cathode material the preparation method comprises the following steps:
Step 1: weighing 0.018mol stannic chloride pentahydrate with 0.016mol sodium hydroxide and be placed in a beaker addition 70mL
Ionized water, magnetic agitation obtain solution A, place it in ice-water bath and stir 30 minutes until being completely dissolved, meanwhile, it weighs
0.018mol white vitriol is placed in another beaker, and 10mL deionized water is added, and magnetic agitation obtains molten until being completely dissolved
Solution B is added in solution A, stirs 12 hours in ice-water bath by liquid B, is centrifuged, obtained solid is washed, dry, obtains forerunner
Body hexahydroxy zinc stannate；
Step 2: the resulting hexahydroxy zinc stannate of step 1 being added in beaker, ultrasound 30 after 20mL deionized water is added
Minute, 0.03mol polyethylene dioxythiophene (PEDOT) (analyzing pure, Aladdin reagent Co., Ltd) is added, magnetic agitation 5 is small
When, products therefrom is centrifuged, obtained solid is washed 3 times, it is dry, obtain black powder；By black powder and 0.075mol sulphur
Powder mixed grinding obtains yellow product C, and yellow product C is put into tube furnace in hydrogen-argon-mixed atmosphere and controls heating rate
600 DEG C of heat preservations are warming up to for 3 DEG C/min and calcine 5h, are then cooled to room temperature with the furnace, are obtained black powder, use mortar grinder
2h to get arrive carbon coating hetero-junctions ZnS/SnS nano particle composite material (referred to as ZHS600C).
Embodiment 4
A kind of anode material of lithium-ion battery is carbon coating hetero-junctions ZnS/SnS nano particle composite material.The sodium
Ion battery cathode material the preparation method comprises the following steps:
Step 1: weighing 0.018mol stannic chloride pentahydrate with 0.016mol sodium hydroxide and be placed in a beaker addition 70mL
Ionized water, magnetic agitation obtain solution A, place it in ice-water bath and stir 30 minutes until being completely dissolved, meanwhile, it weighs
0.018mol white vitriol is placed in another beaker, and 10mL deionized water is added, and magnetic agitation obtains molten until being completely dissolved
Solution B is added in solution A, stirs 12 hours in ice-water bath by liquid B, is centrifuged, obtained solid is washed, dry, obtains forerunner
Body hexahydroxy zinc stannate；
Step 2: the resulting hexahydroxy zinc stannate of step 1 being added in beaker, ultrasound 30 after 20mL deionized water is added
Minute, 0.03mol polyethylene dioxythiophene (PEDOT) (analyzing pure, Aladdin reagent Co., Ltd) is added, magnetic agitation 5 is small
When, products therefrom is centrifuged, obtained solid is washed 3 times, it is dry, obtain black powder；By black powder and 0.075mol sulphur
Powder mixed grinding obtains yellow product C, and yellow product C is put into tube furnace in hydrogen-argon-mixed atmosphere and controls heating rate
700 DEG C of heat preservations are warming up to for 3 DEG C/min and calcine 5h, are then cooled to room temperature with the furnace, are obtained black powder, use mortar grinder
2h to get arrive carbon coating hetero-junctions ZnS/SnS nano particle composite material (referred to as ZHS700C).
Embodiment 5
A kind of anode material of lithium-ion battery is carbon coating hetero-junctions ZnS/SnS nano particle composite material.The sodium
Ion battery cathode material the preparation method comprises the following steps:
Step 1: weighing 0.018mol stannic chloride pentahydrate and 0.016mol sodium hydroxide is placed in a beaker and 0.018mL is added
Deionized water, magnetic agitation obtain solution A, place it in ice-water bath and stir 30 minutes until being completely dissolved, meanwhile, it weighs
0.018mol white vitriol is placed in another beaker, and 10mL deionized water is added, and magnetic agitation obtains molten until being completely dissolved
Solution B is added in solution A, stirs 12 hours in ice-water bath by liquid B, is centrifuged, obtained solid is washed, dry, obtains forerunner
Body hexahydroxy zinc stannate；
Step 2: by the resulting hexahydroxy zinc stannate of step 1 and 0.075mol sulphur powder mixed grinding, yellow product C is obtained,
It is that 3 DEG C/min is warming up to 500 DEG C of heat preservations and forges that yellow product C, which is put into tube furnace to control heating rate in hydrogen-argon-mixed atmosphere,
5h is burnt, room temperature is then cooled to the furnace, obtains black powder, arrives ZnS/SnS nano-particles reinforcement using mortar grinder 2h
Material (referred to as ZHS500).
Using Bruker company model is the X-ray diffractometer of D8ADVANCE type to obtained in above-described embodiment 1
ZHS400C composite negative pole material；Embodiment 2 obtains ZHS500C composite negative pole material；The ZHS600C Compound Negative that embodiment 3 obtains
Pole material；Embodiment 4 obtains ZHS700C composite negative pole material and is tested respectively, and obtained XRD diagram is as shown in Figure 1, from figure
In it can be seen that synthesis all samples have identical diffraction maximum, with standard PDF card compare, all samples all have orthogonal
Crystal structure, and with the promotion of sintering temperature, the peak intensity of diffraction maximum has apparent enhancing.Illustrate higher sintering temperature
Its crystallinity can be made to increase.
With 20 type transmission electron microscope of FEI TecnaiG2 to the resulting hexahydroxy zinc stannate of embodiment 2 and ZHS500C
Composite negative pole material carries out transmissioning electric mirror test, and resulting TEM schemes the preceding body as shown in Fig. 2, synthesized by as can be seen from Figure 2
Body has the structure of cubic block, and ZHS500C has the hetero-junctions composite construction of stannous sulfide zinc sulphide, and has depositing for carbon-coating
In the bulk effect that can effectively limit metal sulfide, achieve the purpose that promote cyclical stability, therefore, the present invention is final
The electrode material with good cycle performance and high rate performance is obtained.
By ZHS400C composite negative pole material obtained in embodiment 1；ZHS500C composite negative pole material is obtained in embodiment 2
Material；ZHS600C composite negative pole material is obtained in embodiment 3；ZHS400C composite negative pole material and embodiment 5 are obtained in embodiment 4
Obtained in ZHS500 composite negative pole material be assembled into the circulation after battery under the 0-2.5V voltage under 500mA/g current density
Test.As a result as shown in figure 3, from figure 3, it can be seen that with cycle-index increase, capacity decayed.And embodiment
The capacity attenuation that ZHS500 material is obtained in 5 obtains the most severe, and ZHS400C composite negative pole material obtained in embodiment 1；It is real
It applies in ZHS500C composite negative pole material and embodiment 3 obtained in example 2 and obtains the capacity attenuation of ZHS600C composite negative pole material
Then greatly reduce.It is steady can also to see that ZHS500C composite negative pole material obtained in embodiment 2 shows good circulation simultaneously
It is qualitative, ZHS400C composite negative pole material obtained in embodiment 1；ZHS500C composite negative pole material obtained in embodiment 2 and
ZHS600C composite negative pole material is obtained in embodiment 3, and there are also 384mAh/g, 502mAh/g, 254mAh/ respectively after 50 circulations
G, the specific capacity of 241mAh/g, it can be seen that pass through the composite negative pole material of the available good cycle of carbon coating, and
When ZHS500C composite material has best cycle performance.
By ZHS400C composite negative pole material obtained in embodiment 1；ZHS500C composite negative pole material is obtained in embodiment 2
Material；ZHS600C composite negative pole material is obtained in embodiment 3；ZHS400C composite negative pole material and embodiment 5 are obtained in embodiment 4
Obtained in ZHS500 composite negative pole material be assembled into battery after carry out ac impedance measurement in occasion China testing impedance equipment.Knot
Fruit is as shown in figure 4, figure 4, it is seen that obtain ZHS500 material in embodiment 5 has maximum impedance, and embodiment 1
Obtained in ZHS400C composite negative pole material；It is obtained in ZHS500C composite negative pole material and embodiment 3 obtained in embodiment 2
The impedance of ZHS600C composite negative pole material then greatly reduces.It can also see that ZHS500C obtained in embodiment 2 is compound simultaneously
Negative electrode material shows the smallest impedance, it can be seen that by carbon coating can with the smaller composite negative pole material of impedance, and
When ZHS500C composite material has the smallest impedance.
Above-mentioned battery assembly method are as follows:
A, cathode pole piece is prepared using the obtained anode material of lithium-ion battery of the present invention as raw material:
0.08g anode material of lithium-ion battery, 0.01gCMC, 0.01g acetylene black are mixed, sodium-ion battery cathode material
Material: CMC: the mass ratio of acetylene black is 8:1:1, and addition 0.1mL deionized water is solvent, is made up of ball grinding stirring and is homogenized
Material, is coated on copper foil, vacuum drying is spare in 100 DEG C of constant temperature ovens；
B, using sodium sheet material as anode pole piece；
C, using above-mentioned positive and negative plate, with containing 3%NaClO4Organic solution (solvent be EC (ethylene carbonate)+
DMC (dimethyl carbonate)+EMC (methyl ethyl ester) mixture, wherein EC:DMC:EMC volume ratio is 1:1:1) as electricity
Liquid is solved, button cell is assembled into.
In conclusion the present invention is a kind of anode material of lithium-ion battery and preparation method thereof, the sodium of above embodiments from
Sub- cell negative electrode material, that is, ZHS (400,500,600,700) C (wherein number represents sintering temperature), when sintering temperature is 500
ZHS500C shows best cycle performance.
Above said content is only the basic explanation under present inventive concept, and is appointed made by technical solution according to the present invention
What equivalent transformation, is within the scope of protection of the invention.
Claims (8)
1. a kind of anode material of lithium-ion battery, which is characterized in that including carbon coating hetero-junctions ZnS/SnS nano-particles reinforcement material
Material.
2. the preparation method of anode material of lithium-ion battery described in claim 1, which comprises the steps of:
Step 1: hexahydroxy zinc stannate being added in reaction vessel, ultrasound after deionized water or dehydrated alcohol is added, is added poly-
Ethene dioxythiophene, glucose or urea, magnetic agitation mixing, products therefrom is centrifuged, obtained solid is washed, dry, is obtained
To black powder；
Step 2: by the resulting black powder of step 1 and sulphur powder, thiocarbamide or thioacetamide mixed grinding, obtaining yellow product；
Step 3: the resulting yellow product of step 2 being put into tube furnace, heating is controlled in hydrogen-argon-mixed or argon atmosphere
Rate is that 1-5 DEG C/min is warming up to 400-700 DEG C of heat preservation calcining 3-8h, then cools to room temperature with the furnace, using mortar grinder, i.e.,
Obtain carbon coating hetero-junctions ZnS/SnS nano particle composite material.
3. the preparation method of anode material of lithium-ion battery as claimed in claim 2, which is characterized in that the calcination temperature
It is 400 DEG C, 500 DEG C, 600 DEG C or 700 DEG C, soaking time 5h.
4. the preparation method of anode material of lithium-ion battery as claimed in claim 2, which is characterized in that in the step 3
Milling time be 1.5~2h.
5. the preparation method of anode material of lithium-ion battery as claimed in claim 2, which is characterized in that in the step 1
Ultrasonic time be 20-40min.
6. the preparation method of anode material of lithium-ion battery as claimed in claim 2, which is characterized in that in the step 1
Magnetic agitation incorporation time be 3-8 hours.
7. the preparation method of anode material of lithium-ion battery as claimed in claim 2, which is characterized in that the hexahydroxy tin
The preparation method of sour zinc includes: to weigh stannic chloride pentahydrate or potassium stannate and sodium hydroxide is placed in reaction vessel and deionization is added
Water, magnetic agitation obtain solution A, place it in ice-water bath and stir 20-40 minutes, weigh seven water sulfuric acid until being completely dissolved
Zinc, which is placed in another reaction vessel, is added deionized water, and magnetic agitation obtains solution B, solution B is added molten until being completely dissolved
It in liquid A, is stirred 10-15 hours in ice-water bath, is centrifuged, obtained solid is washed, it is dry, obtain presoma hexahydroxy stannic acid
Zinc.
8. the preparation method of anode material of lithium-ion battery as claimed in claim 7, which is characterized in that the five water tetrachloros
Change tin or potassium stannate, white vitriol, sulphur powder, thiocarbamide or thioacetamide and polyethylene dioxythiophene, glucose or urea
Molar ratio be 1:1:2-4.2:0.05-1.67.
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| CN110690438A (en) * | 2019-10-21 | 2020-01-14 | 大同新成新材料股份有限公司 | Battery negative electrode material based on metal sulfide composite material and intelligent preparation method thereof |
| CN111710849A (en) * | 2020-07-08 | 2020-09-25 | 广西师范大学 | ZnS/SnS @ NC hollow microsphere anode material for lithium ion/sodium ion battery anode and preparation method thereof |
| CN112397699A (en) * | 2020-11-16 | 2021-02-23 | 西北大学 | Transition metal chalcogenide/carbon composite material rich in anion vacancies and preparation method and application thereof |
| CN113097464A (en) * | 2021-03-31 | 2021-07-09 | 新疆大学 | ZnS-SnS @3DC composite material and preparation method and application thereof |
| CN113097464B (en) * | 2021-03-31 | 2023-03-10 | 新疆大学 | ZnS-SnS @3DC composite material and preparation method and application thereof |
| CN113381012A (en) * | 2021-07-02 | 2021-09-10 | 北京化工大学 | MXene-based metal sulfide and preparation method and application thereof |
| CN114229884A (en) * | 2021-10-28 | 2022-03-25 | 广东邦普循环科技有限公司 | Metal sulfide sodium ion battery cathode material and preparation method thereof |
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| CN114920283A (en) * | 2022-03-29 | 2022-08-19 | 中北大学 | Zinc-tin binary sulfide/carbon nano cubic composite material and preparation method thereof |
| CN114920283B (en) * | 2022-03-29 | 2024-01-26 | 中北大学 | Zinc-tin binary sulfide/carbon nano-cube composite material and preparation method thereof |
| CN114538517A (en) * | 2022-03-31 | 2022-05-27 | 洛阳师范学院 | Mo2C and carbon-sandwiched molybdenum-based heterostructure material and preparation method and application thereof |
| CN114538517B (en) * | 2022-03-31 | 2023-12-22 | 洛阳师范学院 | Mo (molybdenum) 2 C and carbon-coated molybdenum-based heterostructure material and preparation method and application thereof |
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