CN107017390B - A kind of preparation method vulcanizing lithium/carbon composite material - Google Patents
A kind of preparation method vulcanizing lithium/carbon composite material Download PDFInfo
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- CN107017390B CN107017390B CN201710247888.2A CN201710247888A CN107017390B CN 107017390 B CN107017390 B CN 107017390B CN 201710247888 A CN201710247888 A CN 201710247888A CN 107017390 B CN107017390 B CN 107017390B
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/22—Alkali metal sulfides or polysulfides
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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
- 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
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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
- H01M4/36—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
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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
- H01M4/36—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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- 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
Abstract
The invention discloses a kind of methods that vulcanization lithium/carbon composite material is prepared in situ; the vulcanization lithium/carbon composite material is using lithium hydride and carbon disulfide as raw material; under inert atmosphere protection; by lithium hydride and carbon disulfide, 1:0.25 10 is mixed in molar ratio; it is placed in reactor; mixture is risen to 50 ~ 800 DEG C with the heating rate of 0.1 ~ 50 DEG C/min, reacts 0 ~ 12 h.After reacting end and cooling down, first collect reactor in gas, then solid product is taken out from reactor under inert atmosphere protection to get to vulcanize lithium/carbon composite material.Using lithium hydride and carbon disulfide, in-situ preparation vulcanizes lithium/carbon composite material to the present invention in a heated condition, realizes one-step method and vulcanization lithium/carbon composite material is prepared in situ, greatly reduce preparation flow.
Description
(1) technical field
The present invention relates to a kind of preparation methods for vulcanizing lithium/carbon composite material.
(2) background technique
The main method of the lithium/carbon composite material of synthesis vulcanization at present has following two method: first method, first will be organic
Object is coated on lithium sulfide surface, then high-temperature calcination makes organic carbon just obtain vulcanization lithium/carbon composite material under atmosphere protection
(L. M. Suo, Y. J. Zhu, F. D. Han, T. Gao, C. Luo, X. L. Fan, Y. S. Hu, C. S.
Wang, Carbon cage encapsulating nano-cluster Li2S by ionic liquid
polymerization and pyrolysis for high performance Li–S batteries, Nano
Energy., 2015,13:467-473)；Second method by lithium sulfide as in tube furnace, then passes through vapour deposition process
Lithium sulfide surface coat one layer of carbon (C. Nan, Z. Lin, H. Liao, M. Song, Y. Li, E.J. Cairns,
Durable Carbon-Coated Li2S Core−Shell Spheres for High Performance Lithium/
Sulfur Cells, J. Am. Chem. Soc., 2014,136:4569-4663).Above-mentioned two classes method requires first to make
Standby lithium sulfide, then carbon coating is carried out, it not only increases preparation flow and also greatly improves preparation cost, these methods are not easy to
Industrialized production.Thus, develop novel, efficient, the low-cost vulcanization lithium/carbon composite material preparation method of one kind with important
Meaning.
(3) summary of the invention
The invention aims to provide a kind of efficient, low cost, lithium sulfide easy to industrialized production/carbon composite wood
The new method of material.
Technical solution of the present invention is illustrated below.
The present invention occurs chemical reaction using lithium hydride and carbon disulfide in a heated condition and generates lithium sulfide/carbon composite wood
Material, specific technical solution are as follows:
The preparation method of the vulcanization lithium/carbon composite material mainly realizes that synthetic method includes following using heating
Step:
(1) under inert atmosphere protection, lithium hydride and carbon disulfide is mixed, reactor is then transferred to and seals；
(2) mixture in reactor is heated to 50 ~ 800 DEG C, and keeps the temperature 0.1 ~ 12 h；
(3) to after reaction, by reactor gas and solid separate, be that lithium sulfide/carbon is multiple after solid is cooling
Condensation material.
In the step (1), the molar ratio of the lithium hydride and carbon disulfide mixture is 1:0.25 ~ 10.
In the step (2), the heating rate when heating is 0.1 ~ 50 DEG C/min.
Compared with prior art, the present invention its advantages are mainly reflected in:
(1) using lithium hydride and carbon disulfide, in-situ preparation vulcanizes lithium/carbon composite material in a heated condition in the present invention,
It realizes one-step method and vulcanization lithium/carbon composite material is prepared in situ, greatly reduce preparation flow.
(2) the method for the present invention it is simple and easy to control, it is efficient, at low cost, be easily industrialized production.
(3) the vulcanization lithium/carbon composite material of the method for the present invention preparation can be applicable to field of lithium ion battery.
(4) Detailed description of the invention
The X-ray diffractogram of vulcanization lithium/carbon composite material prepared by Fig. 1 embodiment of the present invention 1；
The transmission electron microscope figure of vulcanization lithium/carbon composite material prepared by Fig. 2 embodiment of the present invention 1；
The scanning electron microscope diagram of vulcanization lithium/carbon composite material prepared by Fig. 3 embodiment of the present invention 1.
(5) specific implementation method
With specific embodiment, technical scheme is described further below, but protection scope of the present invention is unlimited
In this.
Embodiment 1
Under an argon atmosphere, 0.0625 mol lithium hydride and 0.066 mol carbon disulfide are added in reactor and close
Envelope.Mixture is risen to 350 DEG C with the heating rate of 1 DEG C/min, keeps the temperature 12 h.After reacting end and cooling down, first collect
Then gas in reactor is taken out solid product from reactor to get multiple to lithium sulfide/carbon under argon atmosphere protection
Condensation material.
Embodiment 2
In a nitrogen atmosphere, 0.05 mol lithium hydride and 0.166 mol carbon disulfide are added in reactor and are sealed.
Mixture is risen to 200 DEG C with the heating rate of 2 DEG C/min, keeps the temperature 6 h.After reacting end and cooling down, reaction is first collected
Then gas in device is taken out solid product under helium atmosphere protection from reactor to get to lithium sulfide/carbon composite wood
Material.
Embodiment 3
Under nitrogen/argon gas mixed atmosphere, 0.125 mol lithium hydride and 0.05 mol carbon disulfide are added to reactor
In and seal.Mixture is risen to 450 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 1 h.After reacting end and cooling down, first
The gas in reactor is collected, is taken out solid product from reactor under then being protected under helium/argon gas mixed atmosphere, i.e.,
Obtain vulcanization lithium/carbon composite material.
Embodiment 4
Under helium atmosphere, 0.1 mol lithium hydride and 0.249 mol carbon disulfide are added in heater and are sealed.
Mixture is risen to 600 DEG C with the heating rate of 10 DEG C/min, keeps the temperature 0.5 h.After reacting end and cooling down, first collect anti-
The gas in device is answered, then takes out solid product to get compound to lithium sulfide/carbon from reactor under helium atmosphere protection
Material.
Embodiment 5
Under an argon atmosphere, 0.25 mol lithium hydride and 0.133 mol carbon disulfide are added in heater and are sealed.
Mixture is risen to 650 DEG C with the heating rate of 15 DEG C/min, keeps the temperature 0.2 h.After reacting end and cooling down, first collect anti-
The gas in device is answered, is taken out solid product from reactor under then being protected under nitrogen/argon gas mixed atmosphere to get to sulphur
Change lithium/carbon composite material.
Embodiment 6
Under an argon atmosphere, 0.2 mol lithium hydride and 0.05 mol carbon disulfide are added in heater and are sealed.It will
Mixture rises to 50 DEG C with the heating rate of 0.1 DEG C/min, keeps the temperature 12 h.After reacting end and cooling down, reaction is first collected
Gas in device takes out solid product under then protecting under nitrogen/argon gas mixed atmosphere from reactor to get to vulcanization
Lithium/carbon composite material.
Embodiment 7
Under an argon atmosphere, 0.1 mol lithium hydride and 1 mol carbon disulfide are added in heater and are sealed.It will mix
It closes object and rises to 800 DEG C with the heating rate of 50 DEG C/min, keep the temperature 0.1 h.After reacting end and cooling down, reactor is first collected
In gas, solid product is taken out from reactor under then being protected under nitrogen/argon gas mixed atmosphere to get to vulcanization
Lithium/carbon composite material.
The preferred embodiments of the invention are only listed above, and protection scope of the present invention is not restricted to this, this field
Made any change is each fallen in the scope of the present invention technical staff within the scope of the invention as claimed.
Claims (2)
1. a kind of preparation method for vulcanizing lithium/carbon composite material: the following steps are included:
(1) under inert atmosphere protection, lithium hydride and carbon disulfide is mixed, reactor is then transferred to and seals, the hydrogen
The molar ratio for changing lithium and carbon disulfide mixture is 1:0.25 ~ 10；
(2) mixture in reactor is heated to 50 ~ 800 DEG C, and keeps the temperature 0.1 ~ 12h；
(3) to after reaction, by reactor gas and solid separate, be lithium sulfide/carbon composite wood after solid is cooling
Material.
2. a kind of preparation method for vulcanizing lithium/carbon composite material as described in claim 1, it is characterised in that: institute in step (2)
The heating rate for the heating stated is 0.1 ~ 50 DEG C/min.
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| CN201710247888.2A CN107017390B (en) | 2017-04-17 | 2017-04-17 | A kind of preparation method vulcanizing lithium/carbon composite material |
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| CN107017390B true CN107017390B (en) | 2019-10-18 |
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| CN112520703B (en) * | 2020-08-03 | 2022-07-22 | 浙江工业大学 | Green preparation method of lithium sulfide |
| CN112520763B (en) * | 2020-08-03 | 2022-04-15 | 浙江工业大学 | Method for preparing lithium sulfide by using lithium sulfate |
| CN112125283A (en) * | 2020-08-03 | 2020-12-25 | 浙江工业大学 | Method for preparing lithium sulfide by solid-liquid mixing and heating |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103764551A (en) * | 2011-06-14 | 2014-04-30 | 罗克伍德锂有限责任公司 | Method for producing a carbon-coated lithium sulfide and use thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103764551A (en) * | 2011-06-14 | 2014-04-30 | 罗克伍德锂有限责任公司 | Method for producing a carbon-coated lithium sulfide and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| A mechanochemical synthesis of submicron-sized Li2S and a mesoporous Li2S/C hybrid for high performance lithium/sulfur battery cathodes;Xiang Li et al.;《 J. Mater. Chem. A》;20170224;第5卷;第6471–6482页 * |
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