CN106953092A - A kind of preparation method of positive material for lithium-sulfur battery - Google Patents
A kind of preparation method of positive material for lithium-sulfur battery Download PDFInfo
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- CN106953092A CN106953092A CN201710243306.3A CN201710243306A CN106953092A CN 106953092 A CN106953092 A CN 106953092A CN 201710243306 A CN201710243306 A CN 201710243306A CN 106953092 A CN106953092 A CN 106953092A
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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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- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
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Abstract
A kind of preparation method of positive material for lithium-sulfur battery, belongs to lithium-sulfur rechargeable battery technical field of material.The preparation method is that the organic molecule pair simultaneously containing element sulphur, metallic element, carbon is sintered under nitrogen or inert gas shielding; the metal sulfide of carbon coating is synthesized, the positive material for lithium-sulfur battery of carbon coating sulphur is then synthesized by oxidizing metal sulfide.Contain while the present invention is used element sulphur, metallic element, carbon organic molecule it is extremely widespread, and industrial products are cheap；Moreover, this kind of method can be sintered by a step and follow-up simple oxidation processes synthesize the sulphur simple substance material of carbon coating, possess extremely strong feasibility and economy.
Description
Technical field
The invention belongs to lithium-sulfur rechargeable battery technical field of material, and in particular to a kind of positive material for lithium-sulfur battery
Preparation method.
Background technology
Constantly increase with the consumption requirements of world energy sources, the petroleum resources increasingly depleted that can be developed, and environment is dirty
Dye is but more serious, how to solve global economic development and has become one to the increase of energy demand and the exacerbation of environmental pollution
Global problem.Therefore storage of the countries in the world to clean energy resourcies such as wind energy, solar energy is recycled, and accelerates electric automobile
The research of replacing fuel oil automobile is increasingly paid attention to；In addition the popularization and application of a large amount of mobile digital electronic equipments；These are required for
Safe, cheap, high-energy-density and long-life secondary cell are realized.
Existing secondary lithium battery is limited by itself theoretical specific capacity to be difficult to meet demand, and fuel cell is in short-term
It is interior also more difficult practical, and the secondary lithium-sulfur battery using elemental sulfur as positive pole is due to very high theoretical energy density
（2500 Whkg-1, 2800 WhL-1）, cheap elemental sulfur, aboundresources and it is environmentally friendly the advantages of, be expected to turn into not
The high-energy-density and long-life secondary cell come.
But, because the low conductivity feature and elemental sulfur of elemental sulfur react numerous intermediate products of generation with lithium（It is many
Sulfide）It is easy to dissolve in electrolyte, the problems such as causing active material loss, self-discharge of battery and electrode passivation, is typically at present
Elemental sulfur is filled in all kinds of carbon class materials with high-specific surface area, high porosity and excellent conductive performance feature, conduction
In macromolecular material, composite is formed, electrolyte is dissolved in and thus caused various to limit polysulfide in cyclic process
Negative effect.
However, common material surface method for coating is to coat organic matter in particle surface, then forge under reducing atmosphere
Burn and form cladding product.But sulphur is calcined can gasify at high temperature, therefore conventional method for coating is not suitable for the carbon coating of sulphur,
The carbon coating of sulphur generally requires extremely harsh capsulation condition, and preparation process is complicated.
The content of the invention
It is an object of the invention to overcome the problem of capsulation condition present in prior art is harsh, preparation process is complicated,
A kind of preparation method of simple efficient positive material for lithium-sulfur battery is provided, this kind of method is by the sulphur simple substance material of carbon coating
Applied to lithium-sulphur cell positive electrode.
Due to it is used while contain sulphur, metal, carbon organic material it is extremely widespread, and industrial products are cheap.And
And, this method can be sintered by a step and subsequently simply oxidation processes synthesize the sulphur simple substance material of carbon coating.Possess extremely strong
Feasibility and economy.
To achieve the above object, the technical scheme that the present invention takes is as follows：
A kind of preparation method of positive material for lithium-sulfur battery, the preparation method is：
Organic molecule pair simultaneously containing element sulphur, metallic element, carbon is sintered under nitrogen or inert gas shielding,
The metal sulfide of carbon coating is synthesized, the lithium-sulfur cell of carbon coating sulphur is then synthesized by oxidizing metal sulfide with just
Pole material.
The present invention is relative to the beneficial effect of prior art：Contain element sulphur, metallic element, carbon member while the present invention is used
The organic molecule of element is extremely widespread, and industrial products are cheap；Moreover, this kind of method can pass through step sintering and follow-up letter
Single oxidation processes synthesize the sulphur simple substance material of carbon coating, possess extremely strong feasibility and economy.
Brief description of the drawings
Fig. 1 is the chemical structural formula figure of organic molecule in the present invention, by taking PZ as an example；
Fig. 2 is the SEM figures for the carbon-clad metal sulfide that embodiment 1 is synthesized；
Fig. 3 is the XRD for the carbon-clad metal sulfide that embodiment 1 is synthesized；
Fig. 4 is the SEM figures for the carbon coating sulfur compound that embodiment 1 is synthesized；
Fig. 5 is the XRD for the carbon coating sulfur compound that embodiment 1 is synthesized；
Fig. 6 is the thermogravimetric curve figure for the carbon coating sulphur simple substance positive electrode that embodiment 1,2,3 is synthesized；
Fig. 7 is the battery performance comparison diagram for the carbon coating sulphur simple substance positive electrode that embodiment 1,2,3 is synthesized.
Embodiment
The technical scheme to invention is further described with reference to the accompanying drawings and examples, but office is not only limitted to this,
It is every technical solution of the present invention to be modified or equivalent, without departing from technical solution of the present invention scope, it all should contain
Cover among protection scope of the present invention.
Embodiment one：What present embodiment was recorded is a kind of preparation method of positive material for lithium-sulfur battery, institute
Stating preparation method is：
Organic molecule pair simultaneously containing element sulphur, metallic element, carbon is sintered under nitrogen or inert gas shielding,
The metal sulfide of carbon coating is synthesized, the lithium-sulfur cell of carbon coating sulphur is then synthesized by oxidizing metal sulfide with just
Pole material.
Embodiment two：A kind of preparation method of positive material for lithium-sulfur battery, institute described in embodiment one
It is one kind in Zn, Fe, Cd, Pb, Cu, Ag or at least two combination to state metallic element.
Embodiment three：A kind of preparation method of positive material for lithium-sulfur battery, institute described in embodiment one
Organic molecule is stated for a class alkylthio carbamic acid metal salt.
Embodiment four：A kind of preparation method of positive material for lithium-sulfur battery, institute described in embodiment one
Inert gas is stated for argon gas.
Embodiment five：A kind of preparation method of positive material for lithium-sulfur battery, institute described in embodiment one
It is 500 ~ 1000 DEG C to state sintering temperature, and heating rate is 1 ~ 10 DEG C/min, and sintering time is 1 ~ 4 h.
Embodiment six：A kind of preparation method of positive material for lithium-sulfur battery, institute described in embodiment one
Oxidant is stated for elemental iodine.
Embodiment seven：A kind of preparation method of positive material for lithium-sulfur battery, institute described in embodiment one
Stating oxidizing process is：The metal sulfide and elemental iodine of carbon coating are dispersed in the mixed solution of second alcohol and water, described carbon
The metal sulfide of cladding and the mass ratio of elemental iodine are 1:6 ~ 12, the volume ratio of second alcohol and water is 1 ~ 5:1, the metal of carbon coating
The ratio of sulfide weight and ethanol volume is：3 g:1 L~8 g:1 L, the reaction temperature of oxidation reaction is 10 ~ 50 DEG C, reaction
Time is 12 ~ 36 h, afterwards, and centrifugation is dried and obtains positive material for lithium-sulfur battery.
Embodiment 1：
The g of PZ 2 is positioned over to take out after 1 h of the lower 500 DEG C of sintering of nitrogen and obtains carbon-clad metal
Sulfide, by the g of carbon-clad metal sulfide 0.2 and the g of elemental iodine 1.2（Mass ratio is 1:6）It is dispersed in second alcohol and water（Volume ratio
For 1:1）The ml of mixed solution 100 in；Reaction temperature is 10 DEG C；Reaction time is centrifugation after 12 h, dries and obtains carbon coating
Sulfur compound.
PZ chemical structural formula described in the present embodiment is as shown in figure 1, the carbon bag of synthesis
The SEM figures of metal sulfide are covered as shown in Fig. 2 XRD is as shown in figure 3, the SEM of the carbon coating sulfur compound of synthesis is schemed such as Fig. 4 institutes
Show, XRD is as shown in Figure 5.As can be seen that can be with by sintering PZ under nitrogen from above-mentioned figure
The metal zinc sulphide of carbon coating, and spatially network structure are obtained, by follow-up oxidizing process, carbon coating sulphur can be obtained
Compound.The carbon-sulfur compound thermogravimetric curve that embodiment 1 is synthesized is as shown in Figure 6.Sulfur content is 65% as seen from the figure.
Embodiment 2：
By two base aminodithioformic acid cadmium 2g be positioned over nitrogen it is lower 1000 DEG C sintering 4h after take out obtain carbon-clad metal sulphur
Compound, by carbon-clad metal sulfide 0.2g and elemental iodine 2.4g（Mass ratio is 1:12）It is dispersed in second alcohol and water（Volume ratio is
5:1）The ml of mixed solution 100 in；Reaction temperature is 50 DEG C；Reaction time is centrifugation after 36 h, dries acquisition carbon sulphur and is combined
Thing.Embodiment it is 2-in-1 into carbon-sulfur compound thermogravimetric curve it is as shown in Figure 6.Sulfur content is 70 % as seen from the figure.
Embodiment 3：
Dibutyl dithiocaarbamate iron 2g is positioned over to take out after the lower 800 DEG C of sintering 3h of nitrogen and obtains carbon-clad metal vulcanization
Thing, by the g of carbon-clad metal sulfide 0.2 and the g of elemental iodine 1.8（Mass ratio is 1:9）It is dispersed in second alcohol and water（Volume ratio is 2:
1）The ml of mixed solution 100 in；Reaction temperature is 25 DEG C；Reaction time is centrifugation after 24 h, dries and obtains carbon-sulfur compound.
The carbon-sulfur compound thermogravimetric curve that embodiment 3 is synthesized is as shown in Figure 6.Sulfur content is 88 % as seen from the figure.
Positive pole is prepared using the carbon-sulfur compound of embodiment 1,2,3 and battery performance test condition is as follows：Using conventional lithium from
Sub- battery electrode preparation method synthesis sulphur simple substance content is 1 mg/cm2Electrode, binding agent is PVDF, and conductive material is activity
Charcoal, three's mass ratio is 8:1:1, three kinds of materials are blended in DMF, scratched after stirring on circular aluminium foil（Aluminium foil diameter：
1.2 cm）, after 60 DEG C of drying, assembling lithium-sulfur cell test, negative pole is metal lithium sheet.The carbon sulphur synthesized using embodiment 1,2,3
The cycle performance that compound prepares the battery of electrode assembling is as shown in Figure 7.As shown in Figure 7, the carbon sulphur that embodiment 1,2,3 is synthesized is answered
Compound initial capacity slightly has difference, but the conservation rate of capacity reaches unanimity, and the slope of curve is similar.Illustrate having for this method synthesis
Although carbon-sulfur compound is because sintering, changes of oxidizing process conditional result in the difference of sulfur content, show unanimously,
Good cyclical stability.
Claims (7)
1. a kind of preparation method of positive material for lithium-sulfur battery, it is characterised in that：The preparation method is：
Organic molecule pair simultaneously containing element sulphur, metallic element, carbon is sintered under nitrogen or inert gas shielding,
The metal sulfide of carbon coating is synthesized, the lithium-sulfur cell of carbon coating sulphur is then synthesized by oxidizing metal sulfide with just
Pole material.
2. a kind of preparation method of positive material for lithium-sulfur battery according to claim 1, it is characterised in that：The metal member
Element is one kind in Zn, Fe, Cd, Pb, Cu, Ag or at least two combination.
3. a kind of preparation method of positive material for lithium-sulfur battery according to claim 1, it is characterised in that：Described organic point
Son is a class alkylthio carbamic acid metal salt.
4. a kind of preparation method of positive material for lithium-sulfur battery according to claim 1, it is characterised in that：The indifferent gas
Body is argon gas.
5. a kind of preparation method of positive material for lithium-sulfur battery according to claim 1, it is characterised in that：The sintering temperature
Spend for 500 ~ 1000 DEG C, heating rate is 1 ~ 10 DEG C/min, sintering time is 1 ~ 4 h.
6. a kind of preparation method of positive material for lithium-sulfur battery according to claim 1, it is characterised in that：The oxidant
For elemental iodine.
7. a kind of preparation method of positive material for lithium-sulfur battery according to claim 6, it is characterised in that：It is described to aoxidize
Cheng Wei：The metal sulfide and elemental iodine of carbon coating are dispersed in the mixed solution of second alcohol and water, the gold of described carbon coating
The mass ratio for belonging to sulfide and elemental iodine is 1:6~1:12, the volume ratio of second alcohol and water is 1:1~5:1, the metal vulcanization of carbon coating
The ratio of thing weight and ethanol volume is：3 g:1 L~8 g:1 L, the metal sulfide of carbon coating and the oxidation reaction of ethanol
Reaction temperature is 10 ~ 50 DEG C, and the reaction time is 12 ~ 36 h, afterwards, and centrifugation is dried and obtains positive material for lithium-sulfur battery.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107834074A (en) * | 2017-11-02 | 2018-03-23 | 四川华昆能源有限责任公司 | A kind of preparation method of lithium-sulfur cell solid state cathode additive and the sulphur negative electrode containing the additive |
| CN109786761A (en) * | 2017-11-10 | 2019-05-21 | 中国科学院大连化学物理研究所 | A kind of zinc-bromine flow battery positive electrode and preparation and application |
| CN109786767A (en) * | 2017-11-10 | 2019-05-21 | 中国科学院大连化学物理研究所 | A kind of zinc-nickel single flow battery positive electrode and its preparation and application |
| CN111063867A (en) * | 2018-10-16 | 2020-04-24 | 中南大学 | Metal thio compound @ S composite material, preparation thereof and application thereof in lithium-sulfur battery |
| CN113666426A (en) * | 2020-05-15 | 2021-11-19 | 中南大学 | Natural sulfide ore-based carbon composite material and preparation method and application thereof |
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| CN106238071A (en) * | 2016-07-11 | 2016-12-21 | 陕西科技大学 | A kind of method using absorption calcination method to prepare ZnS@C composite |
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| CN102671590A (en) * | 2012-05-23 | 2012-09-19 | 上海海事大学 | Preparation method of carbon coated magnetic nano-spherical iron sulfide |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107834074A (en) * | 2017-11-02 | 2018-03-23 | 四川华昆能源有限责任公司 | A kind of preparation method of lithium-sulfur cell solid state cathode additive and the sulphur negative electrode containing the additive |
| CN109786761A (en) * | 2017-11-10 | 2019-05-21 | 中国科学院大连化学物理研究所 | A kind of zinc-bromine flow battery positive electrode and preparation and application |
| CN109786767A (en) * | 2017-11-10 | 2019-05-21 | 中国科学院大连化学物理研究所 | A kind of zinc-nickel single flow battery positive electrode and its preparation and application |
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| CN111063867A (en) * | 2018-10-16 | 2020-04-24 | 中南大学 | Metal thio compound @ S composite material, preparation thereof and application thereof in lithium-sulfur battery |
| CN111063867B (en) * | 2018-10-16 | 2021-04-20 | 中南大学 | Metal thio compound @ S composite material, preparation thereof and application thereof in lithium-sulfur battery |
| CN113666426A (en) * | 2020-05-15 | 2021-11-19 | 中南大学 | Natural sulfide ore-based carbon composite material and preparation method and application thereof |
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