CN109301235A - ZnS@SiO2The preparation of/C high-performance cathode and its storage lithium/sodium application - Google Patents

ZnS@SiO2The preparation of/C high-performance cathode and its storage lithium/sodium application Download PDF

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CN109301235A
CN109301235A CN201811216539.5A CN201811216539A CN109301235A CN 109301235 A CN109301235 A CN 109301235A CN 201811216539 A CN201811216539 A CN 201811216539A CN 109301235 A CN109301235 A CN 109301235A
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zns
sio
sodium
performance
lithium
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蒋建
刘娅妮
朱建慧
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Southwest University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention relates to high-performance ZnS@SiO2The preparation and its storage lithium/sodium application of/C composite negative pole material.Poor circulation problem caused by becoming homeless during storing up lithium/sodium because of volume expansion, dissolution/diffusion flow for sulfide (such as ZnS), we realize nucleocapsid ZnS SiO by simple liquid phase reactor and vapour deposition process using raw materials such as zinc salt, ethyl alcohol and cullet2/ C nano composite material.Compared to ZnS cathode, main advantage are as follows: outer layer SiO2/ C-structure is stablized, and strain resistant ability is strong；Quality specific gravity is low and thickness is thin, and ion/electron-transport impedance is small；It is cheap and easy to get to prepare raw material, the technological process of production is simple；When being used as lithium/sodium-ion battery cathode, ZnS@SiO2/ C shows splendid chemical property.The material preparation approach is novel, effective, ingenious, can sufficiently realize the recycling of glass resource, and the development for high-performance sulfide cathode provides effective foundation.

Description

ZnS@SiO2The preparation of/C high-performance cathode and its storage lithium/sodium application
Technical field
The invention belongs to lithium ions and sodium-ion battery technical field, and in particular to a kind of nucleocapsid ZnS@SiO2/ C Compound Negative The preparation method and application of pole material.
Background technique
With the popularization and application of green novel energy source, develops electrochemical energy conversion and received significant attention with storage device. Compared to other batteries (such as fuel cell, alkaline battery, lead-acid battery), lithium/sodium-ion battery has significant electrification Learn energy storage advantage.Lithium ion battery has the characteristics that energy density is big, output voltage is high, long circulation life and environmental-friendly, extensively It is general apply portable device and in terms of, and sodium-ion battery then relies on the sodium element rich content (earth's crust Middle metal element content occupies the 4th), and have many advantages, such as similar physically and electrically chemical property with lithium ion battery, gradually Research hotspot as energy storage field.However, the fast development in the fields such as high-tech electronic product, electric car and smart grid Propose more harsh performance requirement to battery system, how to be improved from material innovation, electrode configuration angularly promoted storage lithium/ Sode cell performance has become current urgently exploration and solves the problems, such as.
In recent years, metal sulfide (such as MoS2、CoS2、FeS、FeS2、NiS、NiCo2S4、In2S3Deng) be attempted and be developed as Store up lithium/sodium negative electrode material.Wherein, ZnS semiconductor material gradually causes concern in energy storage field, because it has higher theory Specific capacity (962.3 mAh g-1), contained Zn and S element toxicity is low and resource reserve is abundant, low in cost.However, ZnS is the same as it Equally there are many defects in its sulfide, such as poor circulation, capacity attenuation are rapidly, and main cause includes: 1. body phases Electrochemical reaction dynamics is poor；2. lithium/sodium ion, during intercalation/deintercalation, ZnS lattice structure changes greatly, easily occur The dusting of electrode structure with fall off, cause specific capacity to reduce；3. the polysulfide generated in electrochemical reaction process dissolves in electricity It solves liquid and is lost, accelerate the decline of battery capacity.Drawbacks described above has seriously constrained ZnS cathode in terms of storing up lithium/sodium Development and application.
To solve the above problems, general institute Maier of German horse et al. proposes a kind of universal method, by sulfide nanoparticle It is dispersed in hollow carbon pipe/three-dimensional grapheme level matrix structure；Central South University Zhang et al. synthesizes by hydro-thermal method Sea urchin shape ZnS@Nano Carbon object；In the recent period, Tongji University Cheng et al. is empty in three dimensions using atomic layer deposition method (ALD) Shape MoS2The TiO of 0.5nm thickness is constructed outside nano-chip arrays2Interface structure.However, these reactors are mostly nano-carbon film knot Structure, although can effectively improve sulfide cathode cycle performance, application request is still not achieved in electrode cycle life, main Though reason is nano-carbon film and has a good electric conductivity, lack enough mechanical stabilities and durability, structure because It for a long time is influenced that serious damage phenomenon easily occurs by electrode interior active force, leads to electrode specific capacity rapid decay, cycle performance The results such as difference.In addition, prepare above-mentioned nano-reactor raw material and technical costs it is higher, it is difficult to popularization and application.
Comprehensively consider, it is proposed that using raw materials such as cheap zinc salt, ethyl alcohol and cullet, by simple liquid phase reactor and Vapour deposition process uniformly constructs the SiO of functionalization outside ZnS2/ C nano shell, to realize high storage lithium/sodium performance nucleocapsid ZnS@ SiO2/ C nano composite negative pole material.Specific experimental method is as follows: firstly, passing through using zinc acetate, thiocarbamide and cullet as raw material Solwution method synthesizes ZnS@Si (OH)4Presoma；Then, ZnS@SiO is obtained by conventional chemical vapor sedimentation2/ C nano is compound Material.The research significance includes: that on the one hand, can promote the electric conductivity of electrode material unit in external carbon coated layer, and then improve Its electrochemical kinetics characteristic；On the other hand, core-shell structure can provide a large amount of space to mitigate lithium/sodium ion and be embedded in active material The volume expansion caused when material.In addition, the structure also can effectively avoid active matter reuniting effect and polysulfide it is molten Solution is lost with diffusion, significantly improves the electrochemical reversibility and cycle performance of material.Our work provides a kind of green ring The material preparation method of guarantor, has practical application foreground and commercial value.
Summary of the invention
In consideration of it, it is an object of the invention to: (1) provide it is a kind of using conventional liquid phase reaction and vapour deposition process realize SiO2Cladding of/the C to ZnS nanosphere；(2) a kind of constructing plan of high-performance lithium/sodium ion full battery is provided.
In order to achieve the above objectives, the invention provides the following technical scheme:
ZnS@SiO2The preparation of/C high-performance cathode and its storage lithium/sodium application, include the following steps:
(1) synthetic material:
(a) ZnS@Si (OH)4The synthesis of presoma: zinc salt and organic salt ultrasound are dissolved in deionized water, and useless glass on a small quantity is added Glass fragment, after heated stirring in water bath reaction, solution is suspended from the colorless and transparent white that becomes, and is used deionized water after cooling Washing, filtering and drying is up to precursor powder；
(b) ZnS@SiO2The synthesis of/C negative electrode material: by ZnS@Si (OH) made from step (1) (a)4Precursor powder uniformly divides It is distributed in inside crucible, crucible is then placed in quartz tube furnace middle region, is obtained under nitrogen atmosphere through vapor deposition reaction To final product ZnS@SiO2/C；
(2) negative electrode tab: the ZnS@SiO that step (1) is obtained is prepared2/ C dusty material, conductive agent, binder press 8:1:1 mass Than being fully ground in the ball mill with organic solvent, then gained slurry is uniformly coated on copper foil with scraper, is dried through vacuum Up to ZnS@SiO after roasting2/ C negative electrode tab；
(3) half-cell assembling and performance detection: by ZnS@SiO2/ C negative electrode tab is transferred in glove box, using 2025 type knob of CR Button cell shell is packaged；
(a) for storage lithium half-cell test, lithium piece is used as to electrode, and 2500 type polypropylene film of Celgard is molten as diaphragm There is 1 M LiPF6And volume ratio is the EC/ DEC mixed liquor of 1:1 as electrolyte；
(b) for storage sodium half-cell test, sodium piece is used as to electrode, and glass fibre is as diaphragm, dissolved with 1M NaClO4And volume Than the EC/ PC mixed liquor for 1:1 as electrolyte；
By negative electrode tab, diaphragm, electrode sequence is successively assembled, the battery after sealing carries out the survey of half-cell performance after shelving 12h Examination；
(4) full battery assembling and performance test:
(a) for storage lithium full battery test, LiFePO4As anode, ZnS@SiO2/ C is used as cathode, and electrolyte is synchronous with diaphragm Suddenly (3) (a)；
(b) for storage sodium full battery test, Na3V2(PO4)3@C is used as anode, ZnS@SiO2/ C be used as cathode, electrolyte and every Film is the same as step 3(b)；
It is successively assembled by negative electrode tab, diaphragm, positive plate sequence, the battery after sealing carries out the survey of full battery performance after shelving 12 h Examination.
Further, zinc salt is two water zinc acetates in the step (1) (a), the thiocarbamide that organic salt is, zinc salt and organic salt Molar ratio is 1:9.6.
Further, in the step (1) (b), the step of vapor deposition reaction under nitrogen atmosphere protection with 10oC min-1Heating rate be warming up to 900oC is slowly introducing ethyl alcohol saturated vapor in air inlet valve position at this time, using air-flow by ethyl alcohol Gas fast speed belt takes out sample after device natural cooling to tube furnace central area and sustained response 1h.
Further, in the step (2), conductive agent is carbon black.
Further, in the step (2), bonding agent PVDF.
Further, in the step (2), organic solvent is N-Methyl pyrrolidone.
The present invention provides a kind of novel and environmental protection SiO2/ C coats the preparation method of ZnS nanosphere and its in lithium/sodium Application on ion battery.Sode cell is still stored up regardless of being applied to storage lithium, the ZnS@SiO2/ C composite negative pole material is shown Stable chemical property and high reversible.This preparation method is simple and efficient, it can be achieved that large-scale production and waste and old resource are returned It receives and utilizes, there is great sustainable development prospect and researching value.
Detailed description of the invention
In order to keep the purpose of the present invention, technical scheme and beneficial effects clearer, the present invention provides following attached drawing and carries out Illustrate:
Fig. 1 is the ZnS@SiO in embodiment 12The scanning electron microscope diagram (a) and X-ray diffraction (XRD) of/C negative electrode material are composed Scheme (b).
Fig. 2 is the ZnS@SiO in embodiment 12The storage lithium half-cell charging and discharging curve figure (a) and circulation of/C negative electrode material are bent Line chart (b).
Fig. 3 is the ZnS@SiO in embodiment 12The storage sodium half-cell charging and discharging curve figure (a) and circulation of/C negative electrode material are bent Line chart (b).
Fig. 4 is the ZnS@SiO in embodiment 22/C(-)//LiFePO4(+) stores up lithium full battery cyclic curve figure (a) and multiplying power Performance map (b).
Fig. 5 is the ZnS@SiO in embodiment 22/C(-)//Na3V2(PO4)3@C (+) storage sodium full battery cyclic curve figure (a) With high rate performance figure (b).
Specific embodiment
Below in conjunction with attached drawing, a preferred embodiment of the present invention will be described in detail.
1 ZnS@SiO of embodiment2The synthesis of/C negative electrode material
(1) ZnS@Si (OH)4The synthesis of presoma: zinc salt and organic salt ultrasound are dissolved in deionized water, and useless glass on a small quantity is added Glass fragment, after heated stirring in water bath reaction, solution is suspended from the colorless and transparent white that becomes, and is used deionized water after cooling Washing, filtering and drying is up to precursor powder；
(2) ZnS@SiO2The synthesis of/C negative electrode material: by ZnS@Si (OH) made from step (1) (a)4Precursor powder uniformly divides It is distributed in inside crucible, crucible is then placed in quartz tube furnace middle region, with 10 under nitrogen atmosphere protectionoC min-1 Heating rate be warming up to 900oC is slowly introducing ethyl alcohol saturated vapor in air inlet valve position at this time, using air-flow by alcohol gas Fast speed belt takes out sample after device natural cooling, obtains final product ZnS to tube furnace central area and sustained response 1h SiO2/C；
Fig. 1 (a) is products therefrom ZnS@SiO2The nanosphere of core-shell structure is presented in the microscopic appearance of/C, surface sample, is averaged Size is about 200 nm；Fig. 1 (b) is ZnS@SiO2X-ray diffraction (XRD) material phase analysis of/C is made as a result, as seen from the figure The sample diffraction peak and ZnS number JCPDS No.05-0566 and SiO obtained2The standard X-ray of number JCPDS No.88-2488 Powder diffraction spectrum accurately matches.No other impurity diffraction maximums occur, and illustrate the ZnS@that high quality can be made by such method SiO2/ C negative electrode material.
Embodiment 2 is with ZnS@SiO2/ C is the storage lithium/sode cell production and test method of cathode
(1) negative electrode tab: the ZnS@SiO that step (1) is obtained is prepared2/ C dusty material, conductive agent, binder press 8:1:1 mass Than being fully ground in the ball mill with organic solvent, then gained slurry is uniformly coated on copper foil with scraper, is dried through vacuum Up to ZnS@SiO after roasting2/ C negative electrode tab；
(2) half-cell assembling and performance detection: by ZnS@SiO2/ C negative electrode tab is transferred in glove box, using 2025 type knob of CR Button cell shell is packaged；
(a) for storage lithium half-cell test, lithium piece is used as to electrode, and 2500 type polypropylene film of Celgard is molten as diaphragm There is 1 M LiPF6And volume ratio is the EC/ DEC mixed liquor of 1:1 as electrolyte；
(b) for storage sodium half-cell test, sodium piece is used as to electrode, and glass fibre is as diaphragm, dissolved with 1M NaClO4And volume Than the EC/ PC mixed liquor for 1:1 as electrolyte；
By negative electrode tab, diaphragm, electrode sequence is successively assembled, the battery after sealing carries out the survey of half-cell performance after shelving 12h Examination；Embodiment result is shown in Fig. 2 and Fig. 3.
(3) full battery assembling and performance test:
(a) for storage lithium full battery test, LiFePO4As anode, ZnS@SiO2/ C is used as cathode, and electrolyte is synchronous with diaphragm Suddenly (2) (a)；
(b) for storage sodium full battery test, Na3V2(PO4)3@C is used as anode, ZnS@SiO2/ C be used as cathode, electrolyte and every Film is the same as step 2(b)；
It is successively assembled by negative electrode tab, diaphragm, positive plate sequence, the battery after sealing carries out the survey of full battery performance after shelving 12 h Examination；Embodiment result is shown in Fig. 4 and Fig. 5.
Fig. 2 (a) is obtained ZnS@SiO2/ C negative electrode material is 100 mA g in current density-1When storage lithium half-cell Charging and discharging curve figure.With the increase of circulating ring number, the charge and discharge platform of battery does not occur significantly to change, battery specific capacity Apparent decaying is not showed, shows the excellent electrochemical kinetics characteristic of the material system；Fig. 2 (b) is ZnS@SiO2/ C is negative Pole material is in 100 mA g-1Storage lithium half-cell cycle performance under constant current density；After 500 circle electrochemistry circulations still So retain 420 mA h g-1Specific capacity, conservation rate is about 83%, shows ZnS@SiO2The quite stable electrification of/C negative electrode material It learns performance and capacity maintains ability.
Fig. 3 (a) is obtained ZnS@SiO2/ C negative electrode material is 0.1 A g in current density-1When storage sodium half-cell Charging and discharging curve figure.With the increase of circulating ring number, the charge and discharge platform of battery does not occur significantly to change, battery specific capacity Apparent decaying is not showed, shows the excellent electrochemical kinetics characteristic of the material system；Fig. 3 (b) is ZnS@SiO2/ C is negative Pole material is in 0.1 A g-1Storage sodium half-cell cycle performance under constant current density；After 200 circle electrochemistry circulations still So retain 305 mA h g-1Specific capacity, coulombic efficiency shows that excellent cyclical stability and charge and discharge are reversible close to 100% Property.
Fig. 4 (a) is obtained ZnS@SiO2/C(-)//LiFePO4(+) stores up lithium full battery in 0.1 A g-1Current density Under cycle life figure, after 500 charge and discharge cycles are tested, the capacity retention ratio of full battery still up to 80%, is sufficiently reflected Its biggish practical application potentiality；Fig. 4 (b) is obtained ZnS@SiO2/C(-)//LiFePO4(+) full battery is in different electric currents High rate performance figure under density；When lithium ion full battery is in 0.1,0.3,0.6,1.2,2.4,4.8 A g-1Current density under, The charging and discharging capacity of battery is respectively 654,580,502,470,420,310 mA h g-1, sufficiently reflect its excellent storage lithium Full battery multiplying power property.
Fig. 5 (a) is obtained ZnS@SiO2/C(-)//Na3V2(PO4)3The cycle performance figure of@C (+) storage sodium full battery. In 0.05 A g-1Under current density, after 200 circle charge and discharge cycles tests, capacity retention ratio still up to 80%, is embodied The storage sodium full battery has very big development space；Fig. 5 (b) is obtained ZnS@SiO2/C(-)//Na3V2(PO4)3@C(+) High rate performance figure of the full battery under different current densities.As shown, it is in 0.05,0.2,0.8,1.6 and 3.2 A g-1Electricity Specific capacity under current density is respectively 110,98,80,70 and 65 mA h g-1, when current density is restored to 0.05 A g-1, than Capability value can reach 101 mA h g-1, it is shown that fabulous high rate performance.

Claims (4)

1.ZnS@SiO2The preparation of/C high-performance cathode and its storage lithium/sodium application, which comprises the steps of:
(1) materials synthesis:
(a) ZnS@Si (OH)4The synthesis of presoma: zinc salt and organic salt ultrasound are dissolved in deionized water, and a small amount of cullet is added Fragment, after heated stirring in water bath reaction, solution is suspended from the colorless and transparent white that becomes, and is washed with deionized water after cooling Filtration drying is washed up to precursor powder；
(b) ZnS@SiO2The synthesis of/C negative electrode material: by ZnS@Si (OH) made from step (1) (a)4Precursor powder uniformly divides It is distributed in inside crucible, crucible is then placed in quartz tube furnace middle region, is obtained under nitrogen atmosphere through vapor deposition reaction To final product ZnS@SiO2/C；
(2) negative electrode tab: the ZnS@SiO that step (1) is obtained is prepared2/ C dusty material, conductive agent, binder press the quality of 8:1:1 Than being fully ground in the ball mill with organic solvent, then gained slurry is uniformly coated on copper foil with scraper, is dried through vacuum Up to ZnS@SiO after roasting2/ C negative electrode tab；
(3) half-cell assembling and performance detection: by ZnS@SiO2/ C negative electrode tab is transferred in glove box, using 2025 type button of CR Formula battery case is packaged；
(a) for storage lithium half-cell test, lithium piece is used as to electrode, and 2500 type polypropylene film of Celgard is molten as diaphragm There is 1 M LiPF6And volume ratio is the ethylene carbonate EC/ diethyl carbonate DEC mixed liquor of 1:1 as electrolyte；
(b) for storage sodium half-cell test, sodium piece is used as to electrode, and glass fibre is as diaphragm, dissolved with 1M NaClO4And volume Than the EC/ propene carbonate PC mixed liquor for 1:1 as electrolyte；
By negative electrode tab, diaphragm, electrode sequence is successively assembled, the battery after sealing carries out the survey of half-cell performance after shelving 12 h Examination；
(4) full battery assembling and performance test:
(a) for storage lithium full battery test, LiFePO4As anode, ZnS@SiO2/ C is used as cathode, and electrolyte is synchronous with diaphragm Suddenly (3) (a)；
(b) for storage sodium full battery test, Na3V2(PO4)3@C is used as anode, ZnS@SiO2/ C is used as cathode, electrolyte and diaphragm With step 3(b)；
It is successively assembled by negative electrode tab, diaphragm, positive plate sequence, the battery after sealing carries out the survey of full battery performance after shelving 12 h Examination.
2. ZnS@SiO as described in claim 12The preparation of/C high-performance cathode and its storage lithium/sodium application, which is characterized in that described Zinc salt is two water zinc acetates in step (1) (a), and organic salt is thiocarbamide, and the molar ratio of zinc salt and organic salt is 1:9.6.
3. ZnS@SiO as described in claim 12The preparation of/C high-performance cathode and its storage lithium/sodium application, which is characterized in that described It is under nitrogen atmosphere protection the step of vapor deposition reaction in step (1) (b) with 10oC min-1Heating rate be warming up to 900 oC is slowly introducing ethyl alcohol saturated vapor in air inlet valve position at this time, using air-flow by alcohol gas fast speed belt into tube furnace Heart district domain and sustained response 1h, take out sample after device natural cooling.
4. ZnS@SiO as described in claim 12The preparation of/C high-performance cathode and its storage lithium/sodium application, which is characterized in that described Conductive agent is carbon black in step (2)；Bonding agent is Kynoar PVDF；Organic solvent isNMethyl pyrrolidone.
CN201811216539.5A 2018-10-18 2018-10-18 ZnS@SiO2The preparation of/C high-performance cathode and its storage lithium/sodium application Withdrawn CN109301235A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110052278A (en) * 2019-06-12 2019-07-26 河南大学 Core-shell structure ZnS@C@MoS2The preparation method and applications of catalyst
CN111987307A (en) * 2020-06-09 2020-11-24 河南大学 Bimetal-based sodium-ion battery cathode material
CN116040677A (en) * 2022-12-12 2023-05-02 国网黑龙江省电力有限公司电力科学研究院 Preparation method of ZnS negative electrode active material of lithium ion battery

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110052278A (en) * 2019-06-12 2019-07-26 河南大学 Core-shell structure ZnS@C@MoS2The preparation method and applications of catalyst
CN111987307A (en) * 2020-06-09 2020-11-24 河南大学 Bimetal-based sodium-ion battery cathode material
CN111987307B (en) * 2020-06-09 2021-06-18 河南大学 Bimetal-based sodium-ion battery cathode material
CN116040677A (en) * 2022-12-12 2023-05-02 国网黑龙江省电力有限公司电力科学研究院 Preparation method of ZnS negative electrode active material of lithium ion battery
CN116040677B (en) * 2022-12-12 2024-08-06 国网黑龙江省电力有限公司电力科学研究院 Preparation method of ZnS negative electrode active material of lithium ion battery

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