CN108767228A - A kind of pair of carbon-based single titanium-based sulphur composite positive pole and preparation method thereof - Google Patents
A kind of pair of carbon-based single titanium-based sulphur composite positive pole and preparation method thereof Download PDFInfo
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- CN108767228A CN108767228A CN201810544513.7A CN201810544513A CN108767228A CN 108767228 A CN108767228 A CN 108767228A CN 201810544513 A CN201810544513 A CN 201810544513A CN 108767228 A CN108767228 A CN 108767228A
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- sulphur composite
- sulphur
- titanium
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000005864 Sulphur Substances 0.000 title claims abstract description 53
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 31
- 239000010936 titanium Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001694 spray drying Methods 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 239000011164 primary particle Substances 0.000 claims abstract description 9
- 238000007873 sieving Methods 0.000 claims abstract description 9
- 229910021384 soft carbon Inorganic materials 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 113
- 239000000203 mixture Substances 0.000 claims description 35
- 230000004927 fusion Effects 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 14
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- 238000012805 post-processing Methods 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 7
- 238000005255 carburizing Methods 0.000 claims description 7
- 239000003960 organic solvent Substances 0.000 claims description 7
- 239000004576 sand Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 235000019441 ethanol Nutrition 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000011295 pitch Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 14
- 238000005516 engineering process Methods 0.000 abstract description 9
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical class [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 abstract description 5
- 229910021385 hard carbon Inorganic materials 0.000 abstract description 3
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 238000005469 granulation Methods 0.000 abstract description 2
- 230000003179 granulation Effects 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 230000010354 integration Effects 0.000 abstract description 2
- 239000012300 argon atmosphere Substances 0.000 description 12
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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 double carbon-based single titanium-based sulphur composite positive poles and preparation method thereof, pass through the process means such as mixed at high speed, spray drying and calcination process first, utilize the decomposition in situ and spray drying granulation control technology of organic carbon source and butyl titanate, it is submicronized single carbon base list titanium-based primary particle is obtained, the micronized spherical sulphur composite material of second particle；Then spongy more nano/micron pore structure hard carbons or soft carbon have been obtained using the pyrolytic of organic carbon source；Finally so that spherical sulphur composite material is incorporated in hard carbon or the porous structure of soft carbon using high energy integration technology, and increase the binding force of the two using aftertreatment technology, and removes oversize using sieving technique and obtain final products.The present invention principal benefits be：Double carbon-based structures can not only improve the electric conductivity of sulphur positive electrode, but also can inhibit the dissolving of more lithium sulfides in charge and discharge process；Single titanium-based structure can not only inhibit the dissolving of more lithium sulfides in charge and discharge process, but also composite material can be made to maintain higher specific capacity.
Description
Technical field
The present invention relates to positive electrode material of lithium secondary cell fields, more particularly to a kind of double carbon-based single titanium-based sulphur anode composite materials
Material and preparation method thereof.
Background technology
The key of popularization and application new-energy automobile is to realize its economy and the convenience used and conventional fuel oil automobile
Quite.There are larger gaps compared with conventional fuel oil automobile for current new-energy automobile, and it is not to promote economy and ease of use
Carry out the Main way of new-energy automobile development in significant period of time.Promote the economy of new-energy automobile and easy-to-use
Property, it is crucial to increase the course continuation mileage of pure electric drive traveling.To increase course continuation mileage, it is necessary to increase carrying electrokinetic cell system and deposit
The energy of storage, under the premise of not dramatically increasing newly energy vehicle weight and volume, it is necessary to improve the ratio energy and energy of power battery
Metric density.《Energy saving and new-energy automobile Technology Roadmap》It is required that：The specific energy density of single battery in 2025 reaches 400Wh/
The specific energy density of kg, the year two thousand thirty single battery reach 500Wh/kg.Existing lithium-ion battery system specific energy density is difficult to
Meet above-mentioned technology requirement, it is therefore necessary to develop novel battery system.
The theoretical specific capacity 1675mAh/g of sulphur system positive electrode, theory are remote high than energy 2600Wh/kg in lithium-sulfur cell
In existing lithium-ion battery system, and it is sulphur rich reserves, environmentally safe, it is very promising a positive electrode,
Domestic many companies and research institution have all put into certain energy in nearly 5 years and have studied it.But sulphur system positive electrode is conductive
Property is poor, and the polysulfide formed in process of intercalation is soluble in electrolyte, limits its extensive use.
Invention content
In order to solve the above technical problem, the present invention provides a kind of double carbon-based single titanium-based sulphur composite positive poles and its systems
Preparation Method, double carbon-based structures can not only improve the electric conductivity of sulphur positive electrode, but also can inhibit more sulphur in charge and discharge process
Change the dissolving of lithium；Single titanium-based structure can not only inhibit the dissolving of more lithium sulfides in charge and discharge process, but also can make composite wood
Material maintains higher specific capacity.
Technical scheme is as follows：A kind of preparation method of double carbon-based single titanium-based sulphur composite positive poles, including such as
Lower step：
1) simple substance sulphur powder, organic carbon source, butyl titanate and organic solvent are uniformly mixed in high-speed mixer and are obtained
Solidliquid mixture I, wherein organic carbon source quality/sulphur powder quality=5%~10%, butyl titanate quality/sulphur powder quality=2%
~5%, organic solvent quality/(sulphur powder quality+organic carbon source quality+butyl titanate quality)=(4~5):1；
2) the solidliquid mixture I is sanded in sand mill, obtains solidliquid mixture II, solidliquid mixture II
Spend D50≤100nm；
3) solidliquid mixture II is spray-dried under an inert atmosphere, spray drying temperature is 150~180 DEG C, is obtained
To material III, III granularity D of material50=9~15 μm, have primary particle submicronized, the micronized spherical structure of second particle；
4) material III is roasted under an inert atmosphere, calcination temperature be 600~700 DEG C, roasting time be 2~
8h, obtains material IV, and material IV is single carbon base list titanium-based sulphur composite material；
5) organic carbon source is carbonized under an inert atmosphere, carburizing temperature be 750~850 DEG C, carbonization time be 4h~
8h, obtains material V, and material V is spongy more nano/micron pore structure hard carbons or soft carbon；
6) material IV and material V are added in fusion machine and carry out high energy fusion, fusion machine rotating speed is 500~800
Rev/min, time of fusion is 4~8h, so that material IV is entered in the porous structure of material V, obtains material VI, wherein material IV
V mass of quality/material=(5~6):1；
7) material VI is post-processed under an inert atmosphere, post-processing temperature is 400~450 DEG C, when post-processing
Between be 2h~4h, obtain material VII, the sieving of material VII obtains final products.
Further：Step 1) is described to have carbon source for polyvinylpyrrolidone or polyethylene glycol.
Further：Step 1) the organic solvent is ethyl alcohol or propyl alcohol.
Further, step 3), 4), 5) He 7) inert atmosphere be nitrogen, argon gas or helium.
Further, the step 5) organic carbon source is glucose, sucrose, polyvinylpyrrolidone, phenolic resin or pitch.
The present invention first by process means such as mixed at high speed, spray drying and calcination process, using organic carbon source and
The decomposition in situ and spray drying granulation control technology of butyl titanate have obtained single carbon base list titanium-based primary particle sub-micron
Change, the micronized spherical sulphur composite material of second particle；Then it has been obtained using the pyrolytic of organic carbon source more microns spongy
Pore structure hard carbon or soft carbon；Finally spherical sulphur composite material is set to incorporate hard carbon or the porous structure of soft carbon using high energy integration technology
In, and using the binding force of both aftertreatment technology increases, and remove oversize using sieving technique and obtain final products.
The present invention principal benefits be：Double carbon-based structures can not only improve the electric conductivity of sulphur positive electrode, but also can inhibit charge and discharge
The dissolving of more lithium sulfides in electric process；Single titanium-based structure can not only inhibit the dissolving of more lithium sulfides in charge and discharge process, but also
Composite material can be made to maintain higher specific capacity.
Description of the drawings
Fig. 1 is the process flow chart of double carbon-based single titanium-based sulphur composite positive pole preparation methods of the invention.
Specific implementation mode
Technical scheme of the present invention is described in detail with reference to embodiments.
Embodiment 1
A kind of preparation method of double carbon-based single titanium-based sulphur composite positive poles, includes the following steps：
1) simple substance sulphur powder 320g, polyvinylpyrrolidone 16g, butyl titanate 6.4g and ethyl alcohol 1369.6 is mixed in high speed
It is uniformly mixed in conjunction machine and obtains solidliquid mixture I；
2) the solidliquid mixture I is sanded in sand mill, obtains solidliquid mixture II, solidliquid mixture II
Spend D50=80nm；
3) solidliquid mixture II is spray-dried in a nitrogen atmosphere, spray drying temperature is 150 DEG C, obtains material
III, III granularity D of material50=9 μm, have primary particle submicronized, the micronized spherical structure of second particle；
4) material III is roasted in a nitrogen atmosphere, calcination temperature is 600 DEG C, and roasting time 8h is obtained
Material IV, material IV are single carbon base list titanium-based sulphur composite material；
5) glucose 1000g is carbonized in a nitrogen atmosphere, carburizing temperature is 750 DEG C, and carbonization time 4h is obtained
Material V, material V are spongy more nano/micron pore structure hard carbons；
6) IV 300g of the material and V 60g of material are added in fusion machine and carry out high energy fusion, fusion machine rotating speed is 500
Rev/min, time of fusion 8h makes material IV enter in the porous structure of material V, obtains material VI；
7) material VI is post-processed in a nitrogen atmosphere, post-processing temperature is 400 DEG C, and finishing time is
4h, obtains material VII, and the sieving of material VII obtains final products.
Embodiment 2
A kind of preparation method of double carbon-based single titanium-based sulphur composite positive poles, includes the following steps：
1) simple substance sulphur powder 320g, polyethylene glycol 32g, butyl titanate 16g and propyl alcohol 1840g are mixed in high-speed mixer
Conjunction uniformly obtains solidliquid mixture I；
2) the solidliquid mixture I is sanded in sand mill, obtains solidliquid mixture II, solidliquid mixture II
Spend D50=80nm；
3) solidliquid mixture II is spray-dried under an argon atmosphere, spray drying temperature is 180 DEG C, obtains material
III, III granularity D of material50=15 μm, have primary particle submicronized, the micronized spherical structure of second particle；
4) material III is roasted under an argon atmosphere, calcination temperature is 700 DEG C, and roasting time 2h is obtained
Material IV, material IV are single carbon base list titanium-based sulphur composite material；
5) sucrose 1000g is carbonized under an argon atmosphere, carburizing temperature is 850 DEG C, and carbonization time 4h obtains object
Material V, material V are spongy more nano/micron pore structure hard carbons；
6) IV 300g of the material and V 60g of material are added in fusion machine and carry out high energy fusion, fusion machine rotating speed is 800
Rev/min, time of fusion 4h makes material IV enter in the porous structure of material V, obtains material VI；
7) material VI is post-processed under an argon atmosphere, post-processing temperature is 450 DEG C, and finishing time is
2h, obtains material VII, and the sieving of material VII obtains final products.
Embodiment 3
A kind of preparation method of double carbon-based single titanium-based sulphur composite positive poles, includes the following steps：
1) simple substance sulphur powder 320g, polyethylene glycol 16g, butyl titanate 16g and propyl alcohol 1408 are mixed in high-speed mixer
Conjunction uniformly obtains solidliquid mixture I；
2) the solidliquid mixture I is sanded in sand mill, obtains solidliquid mixture II, solidliquid mixture II
Spend D50=80nm；
3) solidliquid mixture II is spray-dried under an argon atmosphere, spray drying temperature is 170 DEG C, obtains material
III, III granularity D of material50=12 μm, have primary particle submicronized, the micronized spherical structure of second particle；
4) material III is roasted under an argon atmosphere, calcination temperature is 700 DEG C, and roasting time 2h is obtained
Material IV, material IV are single carbon base list titanium-based sulphur composite material；
5) polyvinylpyrrolidone 1000g is carbonized under an argon atmosphere, carburizing temperature is 850 DEG C, carbonization time
For 4h, material V is obtained, material V is spongy more nano/micron pore structure hard carbons；
6) IV 300g of the material and V 60g of material are added in fusion machine and carry out high energy fusion, fusion machine rotating speed is 800
Rev/min, time of fusion 4h makes material IV enter in the porous structure of material V, obtains material VI；
7) material VI is post-processed under an argon atmosphere, post-processing temperature is 450 DEG C, and finishing time is
2h, obtains material VII, and the sieving of material VII obtains final products.
Embodiment 4
A kind of preparation method of double carbon-based single titanium-based sulphur composite positive poles, includes the following steps：
1) by simple substance sulphur powder 320g, polyvinylpyrrolidone 32g, butyl titanate 6.4g and propyl alcohol 1433.6g in high speed
It is uniformly mixed in mixing machine and obtains solidliquid mixture I；
2) the solidliquid mixture I is sanded in sand mill, obtains solidliquid mixture II, solidliquid mixture II
Spend D50=80nm；
3) solidliquid mixture II is spray-dried under an argon atmosphere, spray drying temperature is 170 DEG C, obtains material
III, III granularity D of material50=10 μm, have primary particle submicronized, the micronized spherical structure of second particle；
4) material III is roasted under an argon atmosphere, calcination temperature is 700 DEG C, and roasting time 2h is obtained
Material IV, material IV are single carbon base list titanium-based sulphur composite material；
5) phenolic resin 1000g is carbonized under an argon atmosphere, carburizing temperature is 850 DEG C, and carbonization time 4h is obtained
To material V, material V is spongy more nano/micron pore structure hard carbons；
6) IV 300g of the material and V 50g of material are added in fusion machine and carry out high energy fusion, fusion machine rotating speed is 800
Rev/min, time of fusion 4h makes material IV enter in the porous structure of material V, obtains material VI；
7) material VI is post-processed under an argon atmosphere, post-processing temperature is 450 DEG C, and finishing time is
4h, obtains material VII, and the sieving of material VII obtains final products.
Embodiment 5
A kind of preparation method of double carbon-based single titanium-based sulphur composite positive poles, includes the following steps：
1) simple substance sulphur powder, polyvinylpyrrolidone, butyl titanate and ethyl alcohol are uniformly mixed in high-speed mixer
To solidliquid mixture I, wherein polyvinylpyrrolidone quality/sulphur powder quality=10%, butyl titanate quality/sulphur powder quality=
2%, organic solvent quality/(sulphur powder quality+polyvinylpyrrolidone quality+butyl titanate quality)=4:1；
2) the solidliquid mixture I is sanded in sand mill, obtains solidliquid mixture II, solidliquid mixture II
Spend D50=80nm；
3) solidliquid mixture II is spray-dried under helium atmosphere, spray drying temperature is 170 DEG C, obtains material
III, III granularity D of material50=10 μm, have primary particle submicronized, the micronized spherical structure of second particle；
4) material III is roasted under helium atmosphere, calcination temperature is 700 DEG C, and roasting time 2h is obtained
Material IV, material IV are single carbon base list titanium-based sulphur composite material；
5) pitch being carbonized under helium atmosphere, carburizing temperature is 850 DEG C, and carbonization time 4h obtains material V,
Material V is spongy more nano/micron pore structure soft carbons；
6) material IV and material V are added in fusion machine and carry out high energy fusion, fusion machine rotating speed is 800 revs/min
Clock, time of fusion 4h make material IV enter in the porous structure of material V, obtain material VI, wherein IV mass of material/material
V mass=6:1；
7) material VI is post-processed under helium atmosphere, post-processing temperature is 450 DEG C, and finishing time is
4h, obtains material VII, and the sieving of material VII obtains final products.
Experimental conditions：
Table 1 lists the cycle for the first time that button cell is made using positive electrode material of lithium secondary cell made from Examples 1 to 5
Specific discharge capacity and cycle life.
The test condition of button cell is LR 2032,0.1C, 1.5~3.0V, vs.Li+/ Li, the charging/discharging apparatus used
For blue electric charge and discharge instrument.
1 first discharge specific capacity of table and cycle life contrast table
The specific volume as can be seen from the data in the table, double carbon-based single titanium-based sulphur composite positive poles produced by the present invention discharge for the first time
Amount has reached 800mAh/g or more, and circulation volume conservation rate has reached 85% or more within 50 weeks, has stronger application performance.
In conclusion present disclosure is not limited in the above embodiments, the knowledgeable people in same area can
Can propose other embodiments easily within the technological guidance's thought of the present invention, but this embodiment is included in this hair
Within the scope of bright.
Claims (6)
1. a kind of preparation method of double carbon-based single titanium-based sulphur composite positive poles, which is characterized in that include the following steps：
1) simple substance sulphur powder, organic carbon source, butyl titanate and organic solvent are uniformly mixed in high-speed mixer and obtain solid-liquid
Mixture I, wherein organic carbon source quality/sulphur powder quality=5%~10%, butyl titanate quality/sulphur powder quality=2%~
5%, organic solvent quality/(sulphur powder quality+organic carbon source quality+butyl titanate quality)=(4~5):1；
2) solidliquid mixture I is sanded in sand mill, obtains solidliquid mixture II, II granularity D of solidliquid mixture50≤
100nm；
3) solidliquid mixture II being spray-dried under an inert atmosphere, spray drying temperature is 150~180 DEG C, obtains material III,
III granularity D of material50=9~15 μm, there is the spherical structure that primary particle is submicronized, second particle is micronized；
4) material III is roasted under an inert atmosphere, calcination temperature is 600~700 DEG C, and roasting time is 2~8h, is obtained
Material IV, material IV are single carbon base list titanium-based sulphur composite material；
5) organic carbon source is carbonized under an inert atmosphere, carburizing temperature is 750~850 DEG C, and carbonization time is 4h~8h, is obtained
To material V, material V is spongy more nano/micron pore structure hard carbons or soft carbon；
6) material IV and material V are added in fusion machine and carry out high energy fusion, fusion machine rotating speed is 500~800 revs/min
Clock, time of fusion are 4~8h, so that material IV is entered in the porous structure of material V, obtain material VI, wherein IV mass of material/
V mass of material=(5~6):1；
7) material VI is post-processed under an inert atmosphere, post-processing temperature is 400~450 DEG C, and finishing time is
2h~4h, obtains material VII, and the sieving of material VII obtains final products.
2. the preparation method of double carbon-based single titanium-based sulphur composite positive poles according to claim 1, which is characterized in that step 1)
The organic carbon source is polyvinylpyrrolidone or polyethylene glycol.
3. the preparation method of double carbon-based single titanium-based sulphur composite positive poles according to claim 1, which is characterized in that step 1)
The organic solvent is ethyl alcohol or propyl alcohol.
4. the preparation method of double carbon-based single titanium-based sulphur composite positive poles according to claim 1, which is characterized in that step
3), 4), 5) He 7) inert atmosphere is nitrogen, argon gas or helium.
5. the preparation method of double carbon-based single titanium-based sulphur composite positive poles according to claim 1, which is characterized in that step 5)
The organic carbon source is glucose, sucrose, polyvinylpyrrolidone, phenolic resin or pitch.
6. double carbon-based single titanium-based sulphur composite positive poles made from Claims 1 to 5 any one of them preparation method.
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