CN107910585A - A kind of preparation method using carbon/sulphur composite positive pole as the battery of cathode - Google Patents

A kind of preparation method using carbon/sulphur composite positive pole as the battery of cathode Download PDF

Info

Publication number
CN107910585A
CN107910585A CN201711096181.2A CN201711096181A CN107910585A CN 107910585 A CN107910585 A CN 107910585A CN 201711096181 A CN201711096181 A CN 201711096181A CN 107910585 A CN107910585 A CN 107910585A
Authority
CN
China
Prior art keywords
carbon
preparation
sulphur
cathode
battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201711096181.2A
Other languages
Chinese (zh)
Inventor
王耀斌
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi Shengmai Petroleum Co Ltd
Original Assignee
Shaanxi Shengmai Petroleum Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi Shengmai Petroleum Co Ltd filed Critical Shaanxi Shengmai Petroleum Co Ltd
Priority to CN201711096181.2A priority Critical patent/CN107910585A/en
Publication of CN107910585A publication Critical patent/CN107910585A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • 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
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention relates to modern batteries industry, and in particular to a kind of preparation method using carbon/sulphur composite positive pole as the battery of cathode.It is a kind of using carbon/sulphur composite positive pole as the preparation method of the battery of cathode, comprise the following steps：The preparation of corncob activated carbon；The preparation of carbon/sulphur anode composite material；And the assembling of battery.The present invention is using corncob as raw material, the corncob activated carbon that is prepared for having high-specific surface area using phosphoric acid activation method, carries out melting compound obtained carbon/sulphur composite positive pole showing good chemical property with elemental sulfur.Using sulphur/corncob absorbent charcoal composite material as cathode, lithium is the lithium-sulfur cell of anode in 0.2 mA/cm2Electric current under first discharge specific capacity be up to 761.2mAh/g, specific discharge capacity still has a 683.2mAh/g after circulation 20 times, and capacity retention ratio is up to 89.75%.Corncob activated carbon is cheap and easy to get at the same time, and carbon material and composite material preparation process are simple, is adapted to industrial applications, has certain development prospect.

Description

A kind of preparation method using carbon/sulphur composite positive pole as the battery of cathode
Technical field
The present invention relates to modern batteries industry, and in particular to a kind of using carbon/sulphur composite positive pole as the battery of cathode Preparation method.
Background technology
In the lithium secondary battery, elemental sulfur is just having the theoretical specific capacity of l672mAh/g, and energy density is up to 2600Wh/kg, is highest in known positive electrode material of lithium secondary cell.And elemental sulfur have cheap, abundance, The advantages that environmentally friendly, become most promising positive electrode material of lithium secondary cell.But the conduction of elemental sulfur Poor performance, the battery assembled using bright sulfur as cathode, its internal resistance is larger, hinders the transmission of electronics so that the utilization rate of active material Reduce.And the more lithium sulfides of discharging product in reacting are soluble in electrolyte so that the electrical conductivity of electrolyte and the profit of active material Degraded with rate, cause the poor circulation of battery.Researchers often add people's porous carbon materials, porous carbon materials into sulfur electrode Adsorbable sulphur and its intermediate product, and the nonconducting drawback of sulfur materials itself is overcome, so that the electrode reaction of sulfur materials Smoothly carry out, substantially increase the cycle performance of battery.Currently, many researchers select ordered mesopore carbon, carbon nanotubes Deng carbon/sulphur cathode carbon material is used as, no small breakthrough is all achieved on charge-discharge property and cyclical stability, can It is that these carbon materials preparation process is more complicated, and cost is higher, limits its industrialized production and application.
The content of the invention
The present invention is directed to propose a kind of preparation method using carbon/sulphur composite positive pole as the battery of cathode.
Technical program of the present invention lies in：
It is a kind of using carbon/sulphur composite positive pole as the preparation method of the battery of cathode, comprise the following steps：
Step 1：The preparation of corncob activated carbon：
（1）After corncob after being sieved with 18 the polished standard screens impregnates 18h with 2.5 impregnating ratios with 70% concentrated phosphoric acid at 100 DEG C Quartz cell is put into be placed in ceramic tube；
（2）Nitrogen flow is adjusted to 40cm3/ min, and activation temperature is heated to the programming rate of 10 DEG C/min, in the temperature The lower insulation 2h of degree；
（3）Stop heating after activation, continue logical nitrogen to in-furnace temperature and be down to room temperature, product is taken out into the hydrochloric acid with 10% 30min is soaked at 90 DEG C；
（4）Liquid is filtered with double-layer filter paper, and with a large amount of distilled water flushings, its pH value is reached 7, is transferred in mortar and does Dry 24h；
（5）The corncob absorbent charcoal material of preparation is fully ground, is filtered with 400 mesh standard sieves, sample is then transferred to sample It is spare in bottle or bag；
Step 2：The preparation of carbon/sulphur anode composite material：
（1）Sublimed sulfur and corncob activated carbon are pressed 3：1 mass ratio mixes, and is fully ground and is uniformly mixed, mixture dress Enter to seal in reaction kettle, the reaction kettle of sealing is placed in chamber type electric resistance furnace and is warming up to 150 DEG C and keeps 5 h, is then heated to 300 DEG C, 3 h of holding, last cooled to room temperature, obtains carbon/sulphur black powder；
（2）Obtained sulphur/carbon composite powder is mixed with super conductive charcoal, Kynoar, material is ground into 3 h； Add NMP, 30 min of stirring that the slurries with certain viscosity are made in the mixture after grinding, slurries are coated uniformly on 20um thickness Aluminum foil current collector on；Dry 2 hs will be sent at 40 DEG C of vacuum drying chamber after coated aluminium foil at ambient temperature naturally dry, 80 DEG C are warming up to again, dry 12 h；After drying, disk and the tabletting of 14 mm are washed into 14mm belt punchers；
Step 3：The assembling of battery：
It is cathode by the composite material positive plate of above-mentioned preparation, metal lithium sheet is anode, and Celgard2300 microporous polypropylene membranes are Membrane, implantation concentration are the bis trifluoromethyl sulfonic acid imide li of 1mol/L, and solvent is glycol dimethyl ether (DME)+1,3- bis- The electrolyte of butyl oxide link (DOL), assembles 2016 type button cells in the glove box full of dry argon gas.
Preferably, the sulphur/carbon composite powder and the mixed proportion of super conductive charcoal, Kynoar are 8:1: 1。
Or preferably, it is characterised in that：Glycol dimethyl ether (DME)+1 is electrolysed with 3- dioxolanes in the solvent The volume ratio of liquid is 1:1.
The technical effects of the invention are that：
The corncob activated carbon of the invention for using corncob as raw material, using phosphoric acid activation method being prepared for that there is high-specific surface area, with Elemental sulfur melt compound obtained carbon/sulphur composite positive pole and shows good chemical property.With sulphur/corncob Absorbent charcoal composite material is cathode, and lithium is the lithium-sulfur cell of anode in 0.2 mA/cm2Electric current under first discharge specific capacity be up to 761.2mAh/g, specific discharge capacity still has a 683.2mAh/g after circulation 20 times, and capacity retention ratio is up to 89.75%.Corncob at the same time Activated carbon is cheap and easy to get, and carbon material and composite material preparation process are simple, is adapted to industrial applications, has certain development prospect.
Embodiment
It is a kind of using carbon/sulphur composite positive pole as the preparation method of the battery of cathode, comprise the following steps：
Step 1：The preparation of corncob activated carbon：
（1）After corncob after being sieved with 18 the polished standard screens impregnates 18h with 2.5 impregnating ratios with 70% concentrated phosphoric acid at 100 DEG C Quartz cell is put into be placed in ceramic tube；
（2）Nitrogen flow is adjusted to 40cm3/ min, and activation temperature is heated to the programming rate of 10 DEG C/min, in the temperature The lower insulation 2h of degree；
（3）Stop heating after activation, continue logical nitrogen to in-furnace temperature and be down to room temperature, product is taken out into the hydrochloric acid with 10% 30min is soaked at 90 DEG C；
（4）Liquid is filtered with double-layer filter paper, and with a large amount of distilled water flushings, its pH value is reached 7, is transferred in mortar and does Dry 24h；
（5）The corncob absorbent charcoal material of preparation is fully ground, is filtered with 400 mesh standard sieves, sample is then transferred to sample It is spare in bottle or bag；
Step 2：The preparation of carbon/sulphur anode composite material：
（1）Sublimed sulfur and corncob activated carbon are pressed 3：1 mass ratio mixes, and is fully ground and is uniformly mixed, mixture dress Enter to seal in reaction kettle, the reaction kettle of sealing is placed in chamber type electric resistance furnace and is warming up to 150 DEG C and keeps 5 h, is then heated to 300 DEG C, 3 h of holding, last cooled to room temperature, obtains carbon/sulphur black powder；
（2）Obtained sulphur/carbon composite powder is mixed with super conductive charcoal, Kynoar, material is ground into 3 h； Add NMP, 30 min of stirring that the slurries with certain viscosity are made in the mixture after grinding, slurries are coated uniformly on 20um thickness Aluminum foil current collector on；Dry 2 hs will be sent at 40 DEG C of vacuum drying chamber after coated aluminium foil at ambient temperature naturally dry, 80 DEG C are warming up to again, dry 12 h；After drying, disk and the tabletting of 14 mm are washed into 14mm belt punchers；
Step 3：The assembling of battery：
It is cathode by the composite material positive plate of above-mentioned preparation, metal lithium sheet is anode, and Celgard2300 microporous polypropylene membranes are Membrane, implantation concentration are the bis trifluoromethyl sulfonic acid imide li of 1mol/L, and solvent is glycol dimethyl ether (DME)+1,3- bis- The electrolyte of butyl oxide link (DOL), assembles 2016 type button cells in the glove box full of dry argon gas；
Wherein, sulphur/carbon composite powder and the mixed proportion of super conductive charcoal, Kynoar are 8:1:1.Second two in solvent The volume ratio of diethylene glycol dimethyl ether (DME)+1 and 3- dioxolanes electrolyte is 1:1.

Claims (3)

  1. A kind of 1. preparation method using carbon/sulphur composite positive pole as the battery of cathode, it is characterised in that：Comprise the following steps：
    Step 1：The preparation of corncob activated carbon：
    （1）After corncob after being sieved with 18 the polished standard screens impregnates 18h with 2.5 impregnating ratios with 70% concentrated phosphoric acid at 100 DEG C Quartz cell is put into be placed in ceramic tube；
    （2）Nitrogen flow is adjusted to 40cm3/ min, and activation temperature is heated to the programming rate of 10 DEG C/min, in the temperature Lower insulation 2h；
    （3）Stop heating after activation, continue logical nitrogen to in-furnace temperature and be down to room temperature, product is taken out into the hydrochloric acid with 10% 30min is soaked at 90 DEG C；
    （4）Liquid is filtered with double-layer filter paper, and with a large amount of distilled water flushings, its pH value is reached 7, is transferred in mortar and does Dry 24h；
    （5）The corncob absorbent charcoal material of preparation is fully ground, is filtered with 400 mesh standard sieves, sample is then transferred to sample It is spare in bottle or bag；
    Step 2：The preparation of carbon/sulphur anode composite material：
    （1）Sublimed sulfur and corncob activated carbon are pressed 3：1 mass ratio mixes, and is fully ground and is uniformly mixed, mixture dress Enter to seal in reaction kettle, the reaction kettle of sealing is placed in chamber type electric resistance furnace and is warming up to 150 DEG C and keeps 5 h, is then heated to 300 DEG C, 3 h of holding, last cooled to room temperature, obtains carbon/sulphur black powder；
    （2）Obtained sulphur/carbon composite powder is mixed with super conductive charcoal, Kynoar, material is ground into 3 h； Add NMP, 30 min of stirring that the slurries with certain viscosity are made in the mixture after grinding, slurries are coated uniformly on 20um thickness Aluminum foil current collector on；Dry 2 hs will be sent at 40 DEG C of vacuum drying chamber after coated aluminium foil at ambient temperature naturally dry, 80 DEG C are warming up to again, dry 12 h；After drying, disk and the tabletting of 14 mm are washed into 14mm belt punchers；
    Step 3：The assembling of battery：
    It is cathode by the composite material positive plate of above-mentioned preparation, metal lithium sheet is anode, and Celgard2300 microporous polypropylene membranes are Membrane, implantation concentration are the bis trifluoromethyl sulfonic acid imide li of 1mol/L, and solvent is glycol dimethyl ether (DME)+1,3- bis- The electrolyte of butyl oxide link (DOL), assembles 2016 type button cells in the glove box full of dry argon gas.
  2. 2. such as a kind of preparation method using carbon/sulphur composite positive pole as the battery of cathode of claim 1, it is characterised in that：Institute The sulphur stated/carbon composite powder and the mixed proportion of super conductive charcoal, Kynoar are 8:1:1.
  3. 3. such as a kind of preparation method using carbon/sulphur composite positive pole as the battery of cathode of claim 1, it is characterised in that：Institute The volume ratio of glycol dimethyl ether (DME)+1 and 3- dioxolanes electrolyte is 1 in the solvent stated:1.
CN201711096181.2A 2017-11-09 2017-11-09 A kind of preparation method using carbon/sulphur composite positive pole as the battery of cathode Withdrawn CN107910585A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711096181.2A CN107910585A (en) 2017-11-09 2017-11-09 A kind of preparation method using carbon/sulphur composite positive pole as the battery of cathode

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711096181.2A CN107910585A (en) 2017-11-09 2017-11-09 A kind of preparation method using carbon/sulphur composite positive pole as the battery of cathode

Publications (1)

Publication Number Publication Date
CN107910585A true CN107910585A (en) 2018-04-13

Family

ID=61843957

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711096181.2A Withdrawn CN107910585A (en) 2017-11-09 2017-11-09 A kind of preparation method using carbon/sulphur composite positive pole as the battery of cathode

Country Status (1)

Country Link
CN (1) CN107910585A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110350177A (en) * 2019-07-12 2019-10-18 太原科技大学 A kind of preparation method of the layered porous carbon of lithium-sulfur cell/sulphur composite positive pole
CN110970665A (en) * 2018-09-29 2020-04-07 江苏师范大学 SnS2Preparation method of/HNTs composite lithium ion battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110970665A (en) * 2018-09-29 2020-04-07 江苏师范大学 SnS2Preparation method of/HNTs composite lithium ion battery
CN110350177A (en) * 2019-07-12 2019-10-18 太原科技大学 A kind of preparation method of the layered porous carbon of lithium-sulfur cell/sulphur composite positive pole

Similar Documents

Publication Publication Date Title
CN104201389B (en) A kind of preparation method of lithium selenium cell positive pole
CN110459755B (en) Sulfur/polypyrrole/graphene/carbon nanotube composite film, preparation method and application thereof
CN105870417B (en) A kind of preparation method of sodium-ion battery tungsten disulfide/carbon nanometer tube negative pole composite
CN108461692A (en) A kind of preparation method of the electrode supporting zeolite imidazole diaphragm of lithium ion battery
CN110336034A (en) A kind of N doping lithium sulfur battery anode material, preparation method and applications
CN113054183A (en) Preparation method of CoNi bimetal organic framework derived carbon-sulfur composite material
CN107834005A (en) Preparation method of lithium-selenium battery composite diaphragm
CN110627136A (en) 3D-NiO/Co3O4Preparation method of/CNT/S composite material and application of/CNT/S composite material in lithium-sulfur battery
CN111864156A (en) Preparation method of metal nitride-metal oxide heterojunction modified diaphragm for lithium-sulfur battery and lithium-sulfur battery comprising diaphragm
CN106784637B (en) A kind of preparation method of high-energy density lithium-sulphur cell positive electrode material
CN112117444A (en) Carbon-coated cobalt sulfide positive electrode material, preparation method, positive electrode and aluminum ion battery
CN104900848A (en) Long-service-life lithium-sulfur battery anode and manufacturing method of lithium-sulfur battery
CN113937274A (en) Metal organic framework composite material and preparation method and application thereof
CN112563586A (en) Method for improving performance of zinc-iodine battery based on halogen bond effect
CN107910585A (en) A kind of preparation method using carbon/sulphur composite positive pole as the battery of cathode
CN113178659B (en) Modified diaphragm, preparation method thereof and lithium-sulfur battery
CN106654182A (en) Manganese dioxide sulfur-carbon positive electrode and preparation method
CN104638264A (en) Preparation method of battery with carbon/sulfur composite anode material as anode
CN107026269B (en) A kind of collector, electrode and diaphragm integral structure and semi liquid state lithium-sulfur cell
CN109888198B (en) Metal intercalation molybdenum oxide material and preparation method and application thereof
CN114069159B (en) Diaphragm based on nitrogen-rich column layer structure MOF, and preparation method and application thereof
CN110137494B (en) Porous hard carbon microsphere material and preparation method thereof, button cell and preparation method thereof
CN111370629A (en) Preparation method of self-supporting functional interlayer of lithium-sulfur battery
CN111916736B (en) Preparation method and application of porous carbon with two-dimensional core-shell structure
CN111900348B (en) Method for preparing silicon-carbon composite material based on ball milling method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication

Application publication date: 20180413

WW01 Invention patent application withdrawn after publication