CN109698303A - A kind of electronic conductive material and its preparation and the application in lithium-sulfur cell coated separator - Google Patents
A kind of electronic conductive material and its preparation and the application in lithium-sulfur cell coated separator Download PDFInfo
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- CN109698303A CN109698303A CN201811464942.XA CN201811464942A CN109698303A CN 109698303 A CN109698303 A CN 109698303A CN 201811464942 A CN201811464942 A CN 201811464942A CN 109698303 A CN109698303 A CN 109698303A
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
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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
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/44—Fibrous material
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
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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 electronic conductive material and its preparations and the application in lithium-sulfur cell coated separator, belong to technical field of energy storage.The coated separator is to coat electronic conductive material coating in the side of common lithium-sulfur cell ceramic diaphragm, test result shows: the lithium-sulfur cell assembled with conventional ceramic diaphragm is compared, the whole chemical property of battery is improved using the lithium-sulfur cell that coated separator of the present invention assembles, the use of coated separator effectively inhibits " the shuttle effect " of lithium-sulfur cell, make battery that there is higher actual specific capacity, improves the coulombic efficiency and cycle performance of battery.
Description
Technical field
The invention belongs to technical field of energy storage, in particular to a kind of electronic conductive material and its preparation and applied in lithium-sulfur cell
Application in layer diaphragm.The coated separator of preparation can be widely applied to sulfenyl technical field of energy storage, especially lithium-sulfur cell.
Background technique
With the prosperity and development of global economy, the gradually quickening of process of industrialization, the energy problem that 21st century faces
Also increasingly severe, the exploitation of novel renewable energy has been very urgent, while environmental problem has become the whole mankind and faces
Challenge, seek the common recognition that novel green energy storage means early have become the whole mankind.In new secondary battery systems numerous at present
In, lithium-sulfur cell successfully attracts by the up to theoretical specific capacity of 1675mAh/g and the theoretical energy density of 2600Wh/Kg
The concern of whole world researchers.In addition to this, the positive electrode sulphur of lithium-sulfur cell also has low in cost, resourceful,
Environmentally protective three big good characteristic.The industrialization prospect for making a general survey of lithium-sulfur cell, due to the composed structure of lithium-sulfur cell and traditional
Lithium ion battery is substantially similar, thus can largely use for reference and use in conventional lithium ion battery research and development and production process
Experience is expected to realize commercial applications in a short time.
Traditional lithium-sulfur cell is made of anode, diaphragm, electrolyte and cathode.The compound of element sulphur has a variety of valences
State usually exists in the electrolytic solution with the polysulfide of multivalent state, and the charge and discharge process of lithium-sulfur cell is typical electrochemistry oxygen
Change reduction process.Although lithium-sulfur cell has extremely good market prospects, excessively complicated electrochemical reaction at present
Certain problems existing for mechanism and lithium-sulfur cell itself, all limit lithium-sulfur cell to varying degrees and are commercialized on a large scale
Using.During lithium-sulfur cell charge and discharge, positive electrode sulphur will appear the Study of Volume Expansion close to 80%.Solid-state simple substance
The density of sulphur is 2.07g/cm3, final product Li2The density of S is 1.66g/cm3, Li is fully converted in elemental sulfur2The condition of S
Under, lithium-sulfur cell will appear apparent Study of Volume Expansion, and this Study of Volume Expansion, which can not only destroy electrode structure, causes electricity
Pond damage, also results in the decaying of lithium-sulfur cell capacity.Elemental sulfur and final product Li2The electronics and ionic conductivity of S is poor.
In the discharge process of lithium-sulfur cell, final discharging product Li2S would generally gather in electrode surface, therefore can be to Li+And e-'s
Migration effect generates interference, and while discharge process voltage rapid decrease, will lead to elemental sulfur cannot be converted into Li totally2S, into
And the capacity of guiding discharge process reduces.Part Li2Therefore S can cannot be oxidized in charging process, this is also resulted in lithium sulphur
During the charge and discharge cycles of battery, Li2S is constantly deposited in positive electrode surface, eventually allows the active material of lithium-sulfur cell continuous
Loss, while battery capacity also can persistently decay.The intermediate discharging product Li of lithium-sulfur cell2Sx(4≤x≤8) are soluble in electricity
Solve liquid.While therefore active material is lost, it is contemplated that the self discharge problem of lithium-sulfur cell.In the charge and discharge of lithium-sulfur cell
In circulation, intermediate discharging product Li2SxVia electrolyte, by positive diffusive migration to cathode, and the lithium metal with cathode
Learn reaction, the Li of generation2SxAnd Li2S can also deposit a part in negative terminal surface, eventually lead to the irreversible loss of active material,
Therefore coulombic efficiency also seems more low.This more sulphions quilt the phenomenon that the positive and negative interpolar of lithium-sulfur cell spreads shuttle back and forth
Referred to as " shuttle effect ".
During the charge and discharge cycles of lithium-sulfur cell, due to the presence of the shuttle effect of polysulfide, cause lithium sulphur electric
The utilization rate of pond active material is very low, although researchers propose miscellaneous solution in terms of positive electrode,
It is that cannot fundamentally solve the problems, such as that the shuttle effect of polysulfide is brought always, therefore many researchers start to consider diaphragm
A possibility that modified.Common diaphragm mainly plays compartmentation in lithium-sulfur cell, while being the transmission channel of ion again, if
Existing diaphragm can be carried out suitably being modified, while guaranteeing that ion transmission is unaffected, and can effectively inhibit polysulfide
Diffusive migration, like that on the contrary can high degree improve lithium-sulfur cell chemical property.Common polypropylene diaphragm aperture exists
Between several hundred nanometers, when membrane surface carries out material modification, if it is possible to cover the aperture on diaphragm, polysulfide is blocked to expand
While dissipating migration, changes and ion transmission is carried out by the material of membrane surface modification, equally can significantly promote lithium-sulfur cell
Chemical property.The Mathiram professor seminar of The University of Texas at Austin, which proposes to introduce between anode and diaphragm, to be led
Electric mortiser layer, experimental study show that this modified method can play good effect to the adsorption recovery of polysulfide, and can
Improve the cycle life and high rate performance (Chem.Commun.2012,48,8817-8819) of lithium-sulfur cell.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method and applications of lithium-sulfur cell coated separator, to alleviate existing lithium
The problem of sulphur battery, the lithium-sulfur cell with coated separator has higher specific discharge capacity, and is able to suppress lithium sulphur
The shuttle effect of battery, improves the coulombic efficiency of battery, improves the cycle performance of battery.
The technical scheme is that
A kind of electronic conductive material, the material are CNx, x range is 0.03~0.05.
A kind of preparation method of the electronic conductive material, wherein the electronic conductive material is by electronic conductive material
Presoma is made by magnesiothermic reduction reaction, and the mass ratio of the electronic conductive material presoma and magnesium is 2:1~4:1, magnesium heat
Reaction temperature is 700 DEG C~850 DEG C, and the reaction time is 2h~6h.
The electronic conductive material presoma be by urea or trithiocyanuric acid one or two by high-temperature calcination and
At the high-temperature calcination reaction temperature is 400 DEG C~550 DEG C, and the reaction time is 6h~12h.
A kind of lithium-sulfur cell coated separator, wherein the lithium-sulfur cell coated separator is respectively base layer, pottery from the bottom to top
Enamel coating and electronic conductive material coating, the electronic conductive material coating include above-mentioned electronic conductive material.
Base layer is membrane for polymer, and membrane for polymer is polypropylene diaphragm, polyethylene diagrams, polypropylene, polyethylene/poly-
One or more of propylene three-layer coating or nonwoven cloth diaphragm, membrane for polymer is with a thickness of 16 μm~20 μm；
The ceramic layer is one of silica, magnesia, calcium oxide or zirconium dioxide or a variety of ceramic powder phases
Bonding is formed, and ceramic layer thickness is 3 μm~6 μm；
The electronic conductive material coating layer thickness is 0.2 μm~10 μm, density 0.02mg/cm2~2mg/cm2。
A kind of preparation method of the lithium-sulfur cell diaphragm, wherein electronic conductive material is prepared into electronics first and is led
Electronic conductive material slurry is coated on the ceramic layer side of the ceramic diaphragm of base layer and ceramic layer composition simultaneously by electric material slurry
It is dry, electronic conduction functional coating is formed uniformly on ceramic diaphragm surface.
The electronic conductive material slurry is prepared as follows: by electronic conductive material, conductive agent Super P, with
And binder 7~8:1 in mass ratio~2:1 is uniformly mixed, and adds solvent；
The solvent is one of water, ethyl alcohol, ethylene glycol or N methyl pyrrolidone solvent or a variety of；The binder
For Kynoar, complete one or more of sodium carboxymethylcellulose pyce or butadiene-styrene latex；
The method of the coating is dipping film, spin-coating, scraper film, curtain coating film, simple tension or two-way drawing
Any one in stretching method, it is that 6h~for 24 hours is dried in vacuo in 40 DEG C~60 DEG C environment that the drying, which is in temperature,.
The coated separator is used for electrochemical energy storage field.
Coated separator of the present invention is applied to electrochemical energy storage field.When assembled battery, the electronic conductive coating is answered
Close to cell positive material.Electronic conductive material uniformly coats again the side for having ceramic coating, is attached to the surface of ceramic coating.
The present invention shows excellent chemical property using the battery of coated separator assembling.
Beneficial effects of the present invention are as follows:
1. raw material sources used in the present invention are extensive, low in cost, stable process conditions are reliable, entire process flow letter
It is single easy, it is suitble to large-scale industrial production.
2. the present invention selects carboritride as main precursor.Carbonaceous material have two-dimensional structure, for coating every
Membrane coat is a selection well.For electronic conductive coating uniform load on ceramic diaphragm, being formed has multiple laminated structure
Carbon barrier layer, adsorbable battery electric discharge the more lithium sulfides of reduzate and secondary use, weaken lithium-sulfur cell " shuttle effect
Answer ", maximally utilize the active material of battery.
3. the lithium-sulfur cell assembles battery using coated separator, the actual capacity of battery can be significantly improved, and circulation is surely
It is qualitative, so that the whole chemical property of battery is had biggish promotion.
Detailed description of the invention
Fig. 1 is lithium-sulfur cell coated separator structural schematic diagram of the present invention；
Fig. 2 be lithium-sulfur cell coated separator pictorial diagram of the present invention, A for coated with the diaphragm after electronic conductive material coating just
Face, C are the diaphragm reverse side after electronic conductive material coating, and B is common diaphragm front, and D is common diaphragm reverse side；
Fig. 3 is electronic conductive material presoma electron microscope made from present example 1；
Fig. 4 is 1 coated separator lithium-sulfur cell specific capacity cyclic curve figure of present example；
Fig. 5 is 2 coated separator lithium-sulfur cell specific capacity cyclic curve figure of present example；
Fig. 6 is 3 coated separator lithium-sulfur cell specific capacity cyclic curve figure of present example.
Specific embodiment
In order to make the objectives, technical solutions and advantages of the present invention clearer, combined with specific embodiments below further
Illustrate technical solution of the present invention, these descriptions are merely illustrative, these embodiments are not to be construed as to technical solution
Limitation.
Embodiment 1
2g urea (Urea) is weighed, 550 DEG C are heated in Muffle furnace and keeps the temperature 6h, the presoma yellow powder that will be obtained
After (Fig. 3 is presoma electron microscope) and magnesium powder are fully ground, it is added in high-temperature kettle according to the ratio of mass ratio 2:1, in crucible furnace
In be heated to 750 DEG C and keep the temperature 2h, be cooled to room temperature out kettle and obtained black powder be placed in 1mol/L hydrochloric acid and remove not
The magnesium powder and magnesium nitride of reaction, stirring are stood for 24 hours, are respectively washed three times with water and ethyl alcohol and are centrifuged drying to get black is arrived
Powdered electronic conductive material CNx, XPS data display x is 0.04.The CN that will be obtainedxWith adhesive Kynoar
(PVDF), conductive agent Super P continues grinding until being sufficiently mixed according to mass ratio 8:1:1, and mixed-powder is placed in ball grinder
In, the N methyl pyrrolidone (NMP) of 2mL is added dropwise, ball grinder is placed on ball milling 2h on planetary ball mill, then ball milling is equal
Even electronic conductive material slurry is unidirectionally coated in 40 DEG C of the side vacuum drying that ceramic diaphragm has ceramic diaphragm with film pulling device
12h is formed with a thickness of 2 μm of conductive coating, the polypropylene polymerization nitride layer that common lithium-sulfur cell ceramic diaphragm base layer is 16 μm,
The Al that ceramic layer is 4 μm2O3Ceramic layer is punched into the disk that diameter is 18mm to which coated separator (coated separator structure chart be made
With pictorial diagram such as Fig. 1 and Fig. 2).
The electronic conductive material CN that will be prepared according to method abovexAfter sulphur powder in mass ratio 4:6 ground and mixed, closed
It is heat-treated under conditions of 155 DEG C of container for 24 hours, by obtained mixture and adhesive PVDF, conductive agent Super P is according to mass ratio
7:2:1 is uniformly mixed, and dropwise addition 2mL NMP is ground to thick be coated uniformly on aluminium foil and is dried to obtain battery pole piece, then will
Battery pole piece is punched into the disk that diameter is 12mm, and the load capacity of sulphur is 0.7mg/cm2。
Using above-mentioned pole piece and diaphragm, by conductive coating side in coated separator close to positive electrode, in inertia glove box
2016 type button cells are inside assembled into, metal lithium sheet is to electrode, and the electrolyte of use is to be dissolved in DOL and DME by LiTFSI
Mixed solution be made, in electrolyte the concentration of LiTFSI be 1mol/L (in electrolyte, the volume ratio of DOL and DME is 1:1,
LiTFSI is bis trifluoromethyl sulfonic acid imide li, and DOL is 1,3-dioxolane, and DME is glycol dimethyl ether), it is assembled into
Battery carries out correlated performance test with Wuhan indigo plant electrical measurement test system CT2001A.Fig. 4 can be seen that its specific capacity after 100 circles circulation
It can achieve 920mAh/g.
Embodiment 2
2g urea (Urea) is weighed, 550 DEG C are heated in Muffle furnace and keeps the temperature 7h, the presoma yellow powder that will be obtained
After being fully ground with magnesium powder, it is added in high-temperature kettle according to the ratio of mass ratio 3:1,750 DEG C is heated in crucible furnace and is kept the temperature
4h is cooled to room temperature out high-temperature kettle and obtained black powder is placed in 1mol/L hydrochloric acid, after standing overnight, with water and ethyl alcohol
It is respectively washed three times and is centrifuged drying, obtains the electronic conductive material CN of black powderx, XPS data display x is 0.04.It will
Obtained CNx, with adhesive Kynoar (PVDF), conductive agent Super P continues grinding until thorough according to mass ratio 8:1:1
Bottom is sufficiently mixed, and mixed-powder is placed in ball grinder, and 2mL N methyl pyrrolidone (NMP) is added dropwise to liquid in thick, general
Ball grinder is placed on ball milling 4h on planetary ball mill, then the electronic conductive material slurry of ball milling is applied to film pulling device
There is 40 DEG C of the side vacuum drying of ceramic diaphragm, forms the conductive coating with a thickness of 2 μm, common lithium-sulfur cell ceramic diaphragm matrix
The polypropylene polymerization nitride layer that layer is 16 μm, the Al that ceramic layer is 4 μm2O3Ceramic layer is punched into the disk that diameter is 18mm to make
Obtain coated separator.
To above electronic conductive material CN obtainedxAfter sulphur powder in mass ratio 4:6 ground and mixed, in closed container
It is heat-treated under conditions of 155 DEG C for 24 hours, by obtained mixture and adhesive PVDF, conductive agent Super P is according to mass ratio 7:2:
1 is uniformly mixed, and dropwise addition 2mL NMP is ground to thick be coated uniformly on aluminium foil and is dried to obtain battery pole piece, then by battery
The load capacity that pole piece is punched into the disk sulphur that diameter is 12mm is 0.7mg/cm2。
Using above-mentioned pole piece and diaphragm, by conductive coating side in coated separator close to positive electrode, in inertia glove box
2016 type button cells are inside assembled into, metal lithium sheet is to electrode, and the electrolyte of use is that 1,3- dioxy is dissolved in by LiTFSI
The mixed solution of penta ring DOL and glycol dimethyl ether DME is made, in electrolyte the concentration of LiTFSI be 1mol/L (in electrolyte,
The volume ratio of DOL and DME is 1:1, and LiTFSI is bis trifluoromethyl sulfonic acid imide li, and DOL is 1,3-dioxolane, and DME is
Glycol dimethyl ether), the battery being assembled into carries out correlated performance test with Wuhan indigo plant electrical measurement test system CT2001A.Fig. 5 can be seen
Out, its specific capacity can achieve 650mAh/g after 100 circle circulations.
Embodiment 3
2g urea (Urea) is weighed, 550 DEG C are heated in Muffle furnace and keeps the temperature 8h, the presoma yellow powder that will be obtained
After being fully ground with magnesium powder, it is added in high-temperature kettle according to the ratio of mass ratio 4:1,850 DEG C is heated in crucible furnace and is kept the temperature
4h is cooled to room temperature out high-temperature kettle and obtained black powder is placed in 1mol/L hydrochloric acid, after standing overnight, with water and ethyl alcohol
It is respectively washed three times and is centrifuged drying, obtains the electronic conductive material CN of black powderx, XPS data display x is 0.03.It will
Obtained CNx, with adhesive Kynoar (PVDF), conductive agent Super P continues grinding until thorough according to mass ratio 8:1:1
Bottom is sufficiently mixed, and mixed-powder is placed in ball grinder, and 2mL N methyl pyrrolidone (NMP) is added dropwise to liquid in thick, general
Ball grinder is placed on ball milling 2h on planetary ball mill, then the electronic conductive material slurry of ball milling is applied to film pulling device
There is 40 DEG C of the side vacuum drying of ceramic diaphragm, forms the conductive coating with a thickness of 2 μm, common lithium-sulfur cell ceramic diaphragm matrix
The polypropylene polymerization nitride layer that layer is 16 μm, the Al that ceramic layer is 4 μm2O3Ceramic layer is punched into the disk that diameter is 18mm to make
Obtain coated separator.
To above electronic conductive material CN obtainedxAfter sulphur powder in mass ratio 4:6 ground and mixed, in closed container
It is heat-treated under conditions of 155 DEG C for 24 hours, the coating material that will be obtained, with adhesive PVDF, conductive agent Super P is according to mass ratio
7:2:1 is uniformly mixed, and dropwise addition NMP is ground to thick be coated uniformly on aluminium foil and is dried to obtain battery pole piece, then by battery
Pole piece is punched into the disk that diameter is 12mm, and the load capacity of sulphur is 0.7mg/cm2。
Using above-mentioned pole piece and diaphragm, by conductive coating side in coated separator close to cell positive material, in inertia hand
Be assembled into 2016 type button cells in casing, metal lithium sheet be to electrode, the electrolyte of use be dissolved in by LiTFSI DOL and
The mixed solution of DME is made, in electrolyte the concentration of LiTFSI be 1mol/L (in electrolyte, the volume ratio of DOL and DME is 1:
1, LiTFSI is bis trifluoromethyl sulfonic acid imide li, and DOL is 1,3-dioxolane, and DME is glycol dimethyl ether), it is assembled into
Battery carry out correlated performance test with Wuhan indigo plant electrical measurement test system CT2001A.Fig. 6 can be seen that its specific volume after 100 circles circulation
Amount still can achieve 676mAh/g.
Technical solution of the present invention is not limited to examples detailed above, and the other embodiments obtained according to the technique and scheme of the present invention are equal
It should fall into claim of the invention.
Claims (9)
1. a kind of electronic conductive material, the material is nitrogen-doped carbon CNx, x range is 0.03~0.05.
2. a kind of preparation method of electronic conductive material described in claim 1, wherein the electronic conductive material is led by electronics
Electric material presoma is made by magnesiothermic reduction reaction, and the mass ratio of the electronic conductive material presoma and magnesium is 2:1~4:
1, magnesium thermit temperature is 700 DEG C~850 DEG C, and the reaction time is 2h~6h.
3. the preparation method of electronic conductive material according to claim 2, wherein the electronic conductive material presoma
It is to be formed by urea or trithiocyanuric acid one or two by high-temperature calcination, the high-temperature calcination reaction temperature is 400 DEG C
~550 DEG C, the reaction time is 6h~12h.
4. a kind of lithium-sulfur cell coated separator, wherein the lithium-sulfur cell coated separator is respectively base layer, ceramics from the bottom to top
Layer and electronic conductive material coating, the electronic conductive material coating include electronic conductive material described in claim 1.
5. lithium-sulfur cell coated separator according to claim 4, wherein base layer is membrane for polymer, membrane for polymer
For polypropylene diaphragm, polyethylene diagrams, polypropylene, polyethylene/one of polypropylene three-layer coating or nonwoven cloth diaphragm or two
Kind or more, membrane for polymer is with a thickness of 16 μm~20 μm；
The ceramic layer is that one of silica, magnesia, calcium oxide or zirconium dioxide or a variety of ceramic powders are bonding
It is formed, ceramic layer thickness is 3 μm~6 μm；
The electronic conductive material coating layer thickness is 0.2 μm~10 μm, density 0.02mg/cm2~2mg/cm2。
6. a kind of preparation method of lithium-sulfur cell diaphragm described in claim 4 or 5, wherein first by electronic conductive material system
The pottery of the standby ceramic diaphragm that at electronic conductive material slurry, electronic conductive material slurry is formed coated on base layer and ceramic layer
Enamel coating side and drying are formed uniformly electronic conduction functional coating on ceramic diaphragm surface.
7. the preparation method of lithium-sulfur cell diaphragm according to claim 6, wherein the electronic conductive material slurry according to
Following method preparation: by electronic conductive material, conductive agent Super P and binder 7~8:1 in mass ratio~2:1 mixing are equal
It is even, add solvent；
The solvent is one of water, ethyl alcohol, ethylene glycol or N methyl pyrrolidone solvent or a variety of；The binder is poly-
Vinylidene completes one or more of sodium carboxymethylcellulose pyce or butadiene-styrene latex；
The method of the coating is dipping film, spin-coating, scraper film, curtain coating film, simple tension or biaxial tension side
Any one in method, it is that 6h~for 24 hours is dried in vacuo in 40 DEG C~60 DEG C environment that the drying, which is in temperature,.
8. a kind of application of claim 4 or 5 lithium-sulfur cell coated separator, it is characterised in that: the coated separator is used for
Electrochemical energy storage field.
9. the application of lithium-sulfur cell coated separator according to claim 8, it is characterised in that: when assembled battery, coated separator
In electronic conductive coating close to cell positive material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111416089A (en) * | 2020-04-10 | 2020-07-14 | 吉林师范大学 | Composite diaphragm for inducing and inhibiting growth of lithium dendrite, preparation method and lithium ion battery using diaphragm |
| CN112490585A (en) * | 2020-11-27 | 2021-03-12 | 南京林业大学 | Ceramic diaphragm for lithium metal battery and preparation method thereof |
| CN115360478A (en) * | 2022-07-13 | 2022-11-18 | 南昌大学 | In-situ grown carbon nanotube type iron phosphate modified lithium-sulfur battery diaphragm and preparation method thereof, and lithium-sulfur battery |
| CN115536034A (en) * | 2022-12-01 | 2022-12-30 | 四川大学 | Carbon-coated basalt material, and preparation method and application thereof |
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| CN106356488A (en) * | 2015-07-13 | 2017-01-25 | 中国科学院金属研究所 | Composite diaphragm for lithium ion battery for lithium-sulfur battery and preparation method and application of composite diaphragm for lithium ion battery |
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| US20180062142A1 (en) * | 2016-08-31 | 2018-03-01 | Tsinghua University | Lithium-sulfur battery separator and lithium-sulfur batteries using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111416089A (en) * | 2020-04-10 | 2020-07-14 | 吉林师范大学 | Composite diaphragm for inducing and inhibiting growth of lithium dendrite, preparation method and lithium ion battery using diaphragm |
| CN112490585A (en) * | 2020-11-27 | 2021-03-12 | 南京林业大学 | Ceramic diaphragm for lithium metal battery and preparation method thereof |
| CN115360478A (en) * | 2022-07-13 | 2022-11-18 | 南昌大学 | In-situ grown carbon nanotube type iron phosphate modified lithium-sulfur battery diaphragm and preparation method thereof, and lithium-sulfur battery |
| CN115360478B (en) * | 2022-07-13 | 2024-03-29 | 南昌大学 | In-situ growth carbon nanotube type ferric phosphate modified lithium sulfur battery diaphragm, preparation method thereof and lithium sulfur battery |
| CN115536034A (en) * | 2022-12-01 | 2022-12-30 | 四川大学 | Carbon-coated basalt material, and preparation method and application thereof |
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