CN107732202A - A kind of preparation method of lithium sulfur battery anode material - Google Patents
A kind of preparation method of lithium sulfur battery anode material Download PDFInfo
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- CN107732202A CN107732202A CN201710957364.2A CN201710957364A CN107732202A CN 107732202 A CN107732202 A CN 107732202A CN 201710957364 A CN201710957364 A CN 201710957364A CN 107732202 A CN107732202 A CN 107732202A
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000010405 anode material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 121
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 105
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 105
- 239000005864 Sulphur Substances 0.000 claims abstract description 95
- 238000000034 method Methods 0.000 claims abstract description 53
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000006185 dispersion Substances 0.000 claims abstract description 30
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 12
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 11
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 11
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 32
- 239000002131 composite material Substances 0.000 claims description 29
- 239000007788 liquid Substances 0.000 claims description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000010276 construction Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000009467 reduction Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 239000000126 substance Substances 0.000 abstract description 11
- 229920001021 polysulfide Polymers 0.000 abstract description 9
- 239000005077 polysulfide Substances 0.000 abstract description 9
- 150000008117 polysulfides Polymers 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 6
- 238000002844 melting Methods 0.000 abstract description 3
- 230000008018 melting Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 15
- 229910002804 graphite Inorganic materials 0.000 description 14
- 239000010439 graphite Substances 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 12
- 229910052717 sulfur Inorganic materials 0.000 description 11
- 239000011593 sulfur Substances 0.000 description 11
- -1 graphite alkene Chemical class 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000001027 hydrothermal synthesis Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical group [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000011149 active material Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000012938 design process Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical class [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052814 silicon oxide Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001216 Li2S Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MWOBKFYERIDQSZ-UHFFFAOYSA-N benzene;sodium Chemical compound [Na].C1=CC=CC=C1 MWOBKFYERIDQSZ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000011263 electroactive material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000006261 foam material Substances 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000007500 overflow downdraw method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000035899 viability Effects 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
- H01M4/364—Composites as mixtures
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention is a kind of preparation method of lithium sulfur battery anode material.This method by will graphene oxide solution and silica dispersions mix after add ammonium hydrogen carbonate, then mix by ball milling and heat melting method the technique of sulphur and prepare sulphur/compound lithium sulfur battery anode material of N doping porous graphene.The pay(useful) load amount of sulphur is low in the lithium sulfur battery anode material prepared instant invention overcomes prior art, polysulfide " shuttle effect " substantially, the Volumetric expansion of lithium-sulfur cell significantly and battery chemical property it is unstable the defects of.
Description
Technical field
Technical scheme is related to a kind of preparation method of the lithium sulfur battery anode material of height ratio capacity, more particularly to
One kind first passes through template and prepares porous nitrogen-doped graphene as sulfur-donor material, recycles ball milling and hot fusion method to mix sulphur preparation
The method of sulphur/compound lithium sulfur battery anode material of porous nitrogen-doped graphene, belongs to technical field of material chemistry.
Background technology
With developing rapidly for the association areas such as portable type electronic product, electric automobile and energy reserves, to the property of battery
Higher and higher requirement can be proposed.Therefore, exploitation is with high-performance, the secondary electricity of low cost and environmentally friendly new type lithium ion
Pond has very important strategic importance.At present, the lithium ion battery theoretical specific capacity having been commercialized is by itself theoretical specific capacity
For 300mAh/g limitation, it is clear that it can not meet the requirement to lithium ion battery practical application quality, and new lithium-sulfur cell
Theoretical specific capacity is about five times of commercial Li-ion batteries theoretical specific capacity
2500Wh/kg), it is considered to be most one of high-energy battery of development potentiality.
However, lithium-sulfur cell still has some crucial problems in practical application.First, at room temperature bright sulfur be electronics and
(electrical conductivity is 5 × 10-30 to the insulator of ionS·cm-1), electronics and ion are using sulphur as the transmission in the positive pole of positive electrode
It is extremely difficult.Second, the more lithium sulfides of intermediate product formed in charge and discharge process are soluble in electrolyte solution, so as to lead
The electroactive material powder of detached and solution loss on positive pole are caused, and the more lithium sulfides dissolved in the electrolytic solution are diffused into lithium metal
On negative pole, and the lithium sulfide for reacting generation is deposited in the surface of negative pole, causes the internal resistance of battery to increase, ultimately results in battery
Capacity attenuation.Third, sulphur and final product Li2S density is different, sulphur positive pole can occur volumetric expansion and fragmentation (expansion ratio is
76%), these can all cause lithium-sulfur cell cyclical stability to be deteriorated.In the prior art, the scheme of raising lithium-sulfur cell performance is
Elemental sulfur and the porous material with high pore structure are carried out by mechanical compound, formation by the method filled, mixed or coat
Anode composite material, so as to improve the cycle performance of the lithium ion conductivity of sulfur-based positive electrode and battery.The porous material is required：
One, there is chemical stability, do not reacted with polysulfide and lithium metal；Two, insoluble in electrolyte；Three, have higher
Lithium ion conductivity.
Graphene it is conductive it is excellent, chemical stability is high, specific surface area is big, mechanical performance is strong and unique two dimension is more
The characteristics of pore network geometry etc. is remarkable, what can simply and easily be carried out forms clad structure with sulphur, is modified using graphene
Lithium-sulfur cell, it is possible to increase the electro-chemical activity of sulphur simple substance, shorten electronics and ion transmission path, limit the molten of polysulfide
Solution, and then improve lithium-sulfur cell overall performance.Prior art on sulphur/grapheme composite positive electrode material research also has been reported that：
CN105609773A reports a kind of preparation method of sulfur doping three-dimensional structure lithium sulfur battery anode material, uses hydro-thermal method with benzene
Sodium sulfonate is that sulphur source generates three-dimensional sulfur doping graphene, and sulfur doping graphene and section's qin are added in 1-METHYLPYRROLIDONE solution
Black ultrasonic reaction forms three-dimensional structure lithium sulfur battery anode material.It is multiple that CN201310153983.8 reports a kind of sulphur-graphene
Structure lithium sulfur battery anode material preparation method is closed, sulphur powder, organic amine dispersion liquid and graphene organic solvent are prepared first, by two
Person is mixed to get the 3rd dispersion liquid, carries out separation of solid and liquid by the way that water or acid solution is added dropwise, finally gives lithium sulfur battery anode material.
CN201610671807.7 reports a kind of preparation method of foamy graphite alkene lithium-sulphur cell positive electrode piece, first by graphene oxide
With the mixed solution that second alcohol and water is scattered in after polyacrylonitrile ball milling mixing, then soak the solution with nickel foam and make graphene oxide
Into nickel foam, by being thermally treated resulting in foamy graphite alkene, sulphur is finally applied to the doping of sample surfaces progress sulphur, obtains lithium
Sulphur cell positive electrode material.CN201710242972.5 reports a kind of preparation method of lithium sulfur battery anode material, is that one kind will
Graphene oxide reduction, boron doping and the step of solvent thermal reaction one are completed, and boron doped graphene/sulphur compound three is prepared by one-step method
The method for tieing up structure lithium sulfur battery anode material.
The prior art of above-mentioned sulphur/grapheme composite positive electrode material, although improving lithium-sulfur cell to a certain extent
Performance, but existing common defects are：The pay(useful) load amount of sulphur is low in positive electrode, polysulfide " shuttle effect " substantially, lithium
The Volumetric expansion of sulphur battery is notable, and the chemical property of battery is unstable, and material yield is low, industrial feasibility
Difference.
The content of the invention
The purpose of the present invention is for insufficient existing for current techniques, there is provided a kind of preparation side of lithium sulfur battery anode material
Method.This method is used as sulfur-donor material, then the technique system for mixing sulphur by ball milling and heat melting method by introducing silicon dioxide microsphere
Standby sulphur/compound lithium sulfur battery anode material of N doping porous graphene.Instant invention overcomes lithium-sulfur cell prepared by prior art
The pay(useful) load amount of sulphur is low in positive electrode, and substantially, the Volumetric expansion of lithium-sulfur cell is notable for polysulfide " shuttle effect "
And battery chemical property it is unstable the defects of.
Technical scheme is used by the present invention solves the technical problem：
A kind of preparation method of lithium sulfur battery anode material, comprises the following steps
The first step, prepare graphene oxide：
Prepare 1~10mg/mL graphene oxide water solution；
Second step, prepare N doping porous graphene：
Solution A, solution B are mixed to get mixed dispersion liquid C, then ammonium hydrogen carbonate is added in mixed dispersion liquid C, is obtained
Mixed dispersion liquid D, and 1~5h of ultrasonic disperse is carried out to mixed dispersion liquid D using ultrasonic wave separating apparatus, obtain containing nitrogen source carbon
The mixed uniformly suspension of graphene oxide-silica of sour hydrogen ammonium, the high pressure for placing it in polytetrafluoroethyllining lining are anti-
Answer in kettle, the hydrothermal reduction 6-24 hours at 100-200 DEG C；After the product that reaction obtains is washed with deionized, carry out true
Empty drying process, obtained nitrogen-doped graphene-silicon dioxide composite material；Then put it into hydrofluoric acid immersion 6~
24h, that is, N doping porous graphene is made；
Wherein, solution A is that concentration is 1~10mg/mL graphene oxide solutions, solution B be concentration be 1~100mg/mL,
A diameter of 10~300nm of microballoon silica dispersions；Volume ratio is solution A：Solution B=1:1~3；Every 10~50mL
0.1~0.5g ammonium hydrogen carbonate is added in mixed dispersion liquid C；
3rd step, prepare sulphur/N doping porous graphene composite construction lithium sulfur battery anode material：
Porous nitrogen-doped graphene made from second step and pure phase nanometer sulphur powder are put into ball grinder, use planetary ball
Grinding machine 3~5h of mixed processing, the mixture obtained after ball milling is put into the tube furnace under nitrogen protection, at 100~200 DEG C
8~24h is heat-treated, obtains sulphur/compound lithium sulfur battery anode material of porous nitrogen-doped graphene；
Wherein, the porous nitrogen-doped graphene of mass ratio：Pure phase nanometer sulphur powder=1: 3~10.
In described second step, ultrasonic disperse is ultrasonic wave separating apparatus, is carried out under 300~650W power.
In described second step, hydrofluoric acid is that mass percent concentration is 5~40%.
In the 3rd described step, the rotating speed of planetary ball mill is 200~600rpm.
The flow of nitrogen is 100~250mL/min in the 3rd described step.
A kind of preparation method of above-mentioned lithium sulfur battery anode material, described graphene preparation process can use many existing
Known technology (such as hummers methods, solid phase/liquid phase are peeled off)；
A kind of preparation method of above-mentioned lithium sulfur battery anode material, involved raw material by commercially available, as
For the silica dispersions of the different-grain diameter of mould material to be commercially available, equipment used and technique are the technologies of the art
Known to personnel.
Beneficial effects of the present invention are as follows：
The present invention is the most in the hydro-thermal method synthesizing graphite alkene prepared employed in porous nitrogen-doped graphene load sulfur materials
Easy and high yield synthesizing mean, is easy to commercially produce；The selected silicon oxide pellets as template are to select meticulously
, silicon oxide pellets are cheap in presently commercially available template, chemical stability is high and heat endurance is high, Hydrothermal Synthesiss process
Middle pore-creating positive effect, pore-creating yardstick controllability are high；In being introduced into of N doping, ammonium hydrogen carbonate is cheap, Hydrothermal Synthesiss
There are the oxy radicals such as-COOH ,-OH during raw material graphene oxide, ammonium hydrogen carbonate introduces N doping effect more in water-heat process
Substantially, herein it is in situ introduce it is well-designed during N doping.
The electric conductivity of graphene is good, but may be not so good as polymer and metal oxide in pore-creating easy degree, still
The electric conductivity of polymer and metal oxide is again too poor, is also huge by the income that graphene is modified to loose structure just because of this
Big, this experimental program passes through ingenious and meticulous design, breaks through suffering, experimental program is simple, yield is big, has industrial production
Prospect.
It is embodied in：
(1) it is few in order to solve active material load capacity in existing lithium sulfur battery anode material in design process of the invention
And active material utilization it is low the problem of, innovatively propose and be combined by template with N-doping technology, pass through hydro-thermal
The step of approach one completes nitrogen-doping and the pore-creating of graphene, then the technique of sulphur is mixed by ball milling and heat melting method, prepares sulphur/nitrogen
The method for adulterating porous graphene composite construction lithium sulfur battery anode material.First, by the structurally-modified of graphene, graphite
Alkene is changed into the loose structure of the present invention by original layer slab organization, is reduced the energy barrier of graphene-structured, is improved
Sulphur enters the efficiency of pore structure during load sulphur；Secondly, N doping porous graphene structure ratio of the invention is general in the prior art
Logical synusia stacked graphene-structured has higher specific surface area, ensure that sulphur can completely into porous graphene inside,
So that its true graphene for carrying sulfur content and being substantially better than traditional general layer shape structure, it is (such as attached that the pay(useful) load amount of sulphur is up to 76%
Fig. 2), the chemical property of lithium sulfur battery anode material is significantly improved, discharge capacity decay very little, circulation are steady in cyclic process
It is qualitative to significantly improve.
(2) in design process of the invention, the structure of carbon in lithium sulfur battery anode material-sulphur composite has been taken into full account
Problem, it is structurally-modified to graphene progress before sulphur is mixed, template is used silica as, graphite is reduced using the step of hydro-thermal method one
Alkene simultaneously carries out N doping and obtains porous nitrogen-doped graphene structure, realizes the regulating microstructure to sulfur-donor material.Using
The method of heat fusing mixes sulphur and causes sulphur even into default micro-nano duct, to effectively forms carbon-sulphur core shell structure, be modified
N doping porous graphene structure effectively sulphur can be coated, while positive electrode electric conductivity is significantly improved, have
Effect solves the Volumetric expansion of lithium-sulfur cell.Therefore, the lithium sulfur battery anode material prepared by the present invention effectively inhibits
Volumetric expansion in charge and discharge process, electric conductivity are significantly improved.
(3) in design process of the invention, the structure of carbon in lithium sulfur battery anode material/sulphur composite has been taken into full account
Control problem, the excellent electrochemical performance of electrode material ensure that by the microstructure control of composite, i.e., mixed by nitrogen
Miscellaneous method, realize the regulating microstructure to carbon/sulphur composite.The present invention is used as nitrogen source and oxidation by the use of ammonium hydrogen carbonate
Graphene, because nitrogen-atoms has stronger absorption electronic capability, may replace portion by hydro-thermal legal system N doping porous graphene
Point carbon atom and do not change the crystal structure of graphene, so as to improve the electric conductivity of carbon material and in charge and discharge process
Polysulfide produces suction-operated, significantly reduces " the shuttle effect " of polysulfide, and then can be effectively improved lithium-sulfur cell
Cycle performance.Therefore, the present invention improves lithium-sulphur cell positive electrode material by controlling the microstructure of lithium sulfur battery anode material
The cycle performance of material.
Compared with prior art, the marked improvement of the inventive method is as follows：
(1) prior art CN201710242972.5 is existing basic scarce during lithium sulfur battery anode material is prepared
Be trapped in：(a) patented technology mixes sulphur using hydro-thermal method original position, makes graphene and sulphur compound in water-heat process, and hydro-thermal mistake
Journey inevitably causes sulphur and graphene each to suspend in water and do not form composite construction, even if the two is combined with each other,
Sulphur is also adhered merely to graphenic surface, and it is not high to cause truly to carry sulfur content, initial capacity height is shown as in cyclic process, but hold
Measure decrease speed quickly, can not effectively solve that active material load capacity is few in existing lithium sulfur battery anode material and active material is sharp
With rate it is low the problem of, it is difficult to realize the discharge stability of lithium-sulfur cell.Importantly, the patent is not tied to graphene
Structure is modified, and graphene remains on original multi-layer sheet structure, the stacking again of graphene synusia is necessarily caused in drying process, is subtracted
Its small specific surface area, it is difficult to solve the Volumetric expansion of lithium-sulfur cell.In addition, the graphene-structured of synusia shape is difficult to have
Effect suppresses the diffusion of sulphur, and the graphene-structured energy barrier of heap poststack is higher, and the difficulty that sulphur enters graphene-structured also accordingly increases
It is high, it is difficult to form the pay(useful) load to sulphur.(b) numerous studies show, graphene has excellent mechanical performance, heat conductivility and led
Electrical property, the chemical property of lithium-sulfur cell can improved after compound with sulphur, but the structure of carbon-sulphur composite can direct shadow
Ring the electric conductivity of lithium sulfur battery anode material and the rejection ability to electrode volume bulking effect.The patented technology takes original position to mix
Sulphur method, the different shadow of reaction energy height needed for different zones during graphene hydrothermal reduction is limited to during mixing sulphur
Ring.It is not the homogeneous number of plies using the graphene oxide improved prepared by Hummers methods, it will usually 2~20 layers are shown as,
Oxygen-containing group's quantity that the graphene oxide of the different numbers of plies is mingled with water-heat process is inevitable also different, and this, which is resulted in, is reacting
During, the energy required for graphene more than the number of plies is more, the little energy required for the few graphene of the number of plies, therefore mixes in the original location
During sulphur, the uneven phenomenon of loading of sulphur can be produced in different zones, causes carbon-sulphur composite fault of construction to be present,
Subregion sulphur is exposed to graphenic surface, reduces the electric conductivity of positive electrode.In summary, the standby lithium sulphur electricity of the patent system
Pond positive electrode is low to the loading of sulphur and loading is uneven, and capacity decrease speed is fast, can not effectively solve existing lithium-sulfur cell
The problem of the problem of active material load capacity is few in positive electrode, utilization rate is low and Volumetric expansion are obvious, poorly conductive.This
Sulphur made from inventive method/compound lithium sulfur battery anode material of N doping porous graphene overcomes prior art completely
Drawbacks described above present in CN201710242972.5.
(2) prior art CN201610671807.7 exists during foamy graphite alkene lithium-sulphur cell positive electrode piece is prepared
Essential defect be：The patent is by the porous of nickel foam material for the structurally-modified of graphene, and mould is used as using it
Plate prepares porous graphene, carries out process of thermal treatment by smearing sulphur powder to complete the compound of sulphur-carbon, the foam not only prepared
There is fault of construction in graphene, and can not also realize using smearing mode the good compound of sulphur and graphene, cause point of sulphur
Cloth is uneven, pay(useful) load amount of the graphene to sulphur be not high, and positive electrode electric conductivity is poor, does not solve lithium-sulphur cell positive electrode material
The shortcomings that expecting low sulphur appendix amount, poorly conductive, obvious shuttle effect.Sulphur/N doping porous graphite made from the inventive method
The compound lithium sulfur battery anode material of alkene overcomes the drawbacks described above present in prior art CN201610671807.7 completely.
(3) prior art CN201310153983.8 is preparing sulphur-graphene composite structure lithium sulfur battery anode material
During existing essential defect be：The patent prepares the lithium sulphur of sulphur-graphene composite structure using the technique of separation of solid and liquid
Cell positive material, during sulphur is mixed, the dispersion in organic solvent of the organic amine dispersion liquid of sulphur and graphene is carried out first
Mixing, then come indigenous graphite alkene-sulfur compound, this indigenous graphite from mixed solution by way of adding water or acid solution
The process of alkene-sulfur compound simply can only be mixed sulphur and graphene, and the load capacity of sulphur is low and uneven；Dropwise addition process
Middle solution concentration is because the precipitation of graphene-sulfur compound constantly reduces, and load sulfur content is significantly different in the sample successively separated out, after
The sample of precipitation carries sulfur content and is significantly lower than the sample first separated out, and this uneven of load sulfur content can cause polysulfide " to shuttle and imitate
Should ", electrode material Volumetric expansion is obvious, stable circulation is poor in charge and discharge process.Sulphur/nitrogen is mixed made from the inventive method
The miscellaneous compound lithium sulfur battery anode material of porous graphene overcomes upper present in prior art CN201310153983.8 completely
State defect.
(4) the inventive method passes through the selection of raw material and ratio regulation and control, the design of the preparation technology and control of implementation process
System, cost is low, yield is high for innovative preparing, constitutionally stable N doping porous graphene, and Industrial Applicability is strong；Pass through
The design and regulation and control of sulphur process are mixed, sulphur is realized and is covered by N doping porous graphene completely, forms stable carbon-sulphur cladding
Type structure, the pay(useful) load amount of sulphur in lithium sulfur battery anode material is significantly improved, such as shown in (accompanying drawing 2), the quality percentage of sulphur
Content about 76%, it effectively prevent " the shuttle effect " of polysulfide and " Volumetric expansion " of lithium-sulfur cell, electrochemistry
The excellent and cyclical stability of energy is extremely strong.
(5) sulphur prepared by the inventive method/compound lithium sulfur battery anode material of N doping porous graphene is as positive pole
The lithium-sulfur cell of the working electrode composition of pole piece, such as shown in (accompanying drawing 4), the first charge-discharge specific capacity of battery reaches under 0.1C
1537mAh/g, has high discharge capacity and remarkable cyclical stability, and its chemical property is substantially better than above-mentioned prior art
Obtained lithium-sulfur cell performance.
(6) present invention is a kind of lithium sulfur battery anode material preparation method for possessing high yield and commercial viability feature.
Brief description of the drawings
The present invention is further described with reference to the accompanying drawings and examples.
The X-ray diffractogram of sulphur/N doping porous graphene composite obtained by Fig. 1 embodiments 1.
Fig. 2 is the thermogravimetric curve figure of sulphur/N doping porous graphene composite obtained by embodiment 1.
Fig. 3 is the electron scanning micrograph of the N doping porous graphene obtained by embodiment 1.
Sulphur/N doping porous graphene composite construction lithium sulfur battery anode materials of the Fig. 4 obtained by embodiment 1 is first
Charge discharge curve.
Embodiment
Embodiment 1：
The first step, prepare graphene oxide：
Prepare 2mg/mL graphene oxide water solution；Wherein, described graphene oxide is well known materials, and the present invention is
Using the graphene oxide being prepared using Hummers methods are improved.Following examples are identical；
Second step, prepare N doping porous graphene：
It is 2mg/mL graphene oxide solutions A by concentration, a diameter of 300nm of concentration 50mg/mL, microballoon titanium dioxide
Silicon dispersion liquid B is 1 by liquor capacity ratio:1 is uniformly mixed to get mixed dispersion liquid C, and 0.5g ammonium hydrogen carbonate is added 50m and mixed and is divided
In dispersion liquid C, mixed dispersion liquid D is obtained, and ultrasonic disperse 5h is carried out to mixed dispersion liquid D using ultrasonic wave separating apparatus, is obtained
The mixed uniformly suspension of graphene oxide-silica containing nitrogen source ammonium hydrogen carbonate, has been placed it in polytetrafluoroethylene (PTFE)
In the autoclave of lining, hydrothermal reduction 12 hours at 200 DEG C；Carried out after the product that reaction obtains is washed with deionized
Vacuum drying treatment, the nitrogen-doped graphene-silicon dioxide composite material obtained after drying is put into mass percent concentration is
24h is soaked in 10% hydrofluoric acid causes the silica spheres as template to be etched away, that is, N doping porous graphene is made
Sample；
3rd step, prepare sulphur/N doping porous graphene composite construction lithium sulfur battery anode material：
Porous nitrogen-doped graphene made from second step and pure phase nanometer sulphur powder are put into ball grinder, use planetary ball
Grinding machine mixed processing 5h, the mixture obtained after ball milling is put into the tube furnace under nitrogen protection, is heat-treated at 150 DEG C
12h, obtain sulphur/compound lithium sulfur battery anode material of porous nitrogen-doped graphene；
Wherein, the porous nitrogen-doped graphene of mass ratio：Pure phase nanometer sulphur powder=1: 4；
In described second step, ultrasonic disperse is ultrasonic wave separating apparatus, is carried out under 650W power.
In the 3rd described step, the rotating speed of planetary ball mill is 400rpm.
The flow of nitrogen is 150mL/min in the 3rd described step.
A kind of preparation method of above-mentioned lithium sulfur battery anode material, described graphene preparation process can use many existing
Known technology (such as hummers methods, solid phase/liquid phase are peeled off)；
A kind of preparation method of above-mentioned lithium sulfur battery anode material, involved raw material by commercially available, as
For the silica dispersions of the different-grain diameter of mould material to be commercially available, equipment used and technique are the technologies of the art
Known to personnel.
Fig. 1 is that X-ray diffraction is tested to obtain data, and sulphur/N doping porous graphene composite is respectively illustrated in figure
(in figure ● shown in curve), N doping porous graphene material (in figure shown in ■ curves) and pure phase nanometer sulphur (in figure ▲ curve
It is shown) X ray diffracting spectrum.It can be seen that along with graphite in sulphur/N doping porous graphene composite pole material
The characteristic peak for showing sulphur of alkene characteristic peak is obvious, shows that sulphur has enriched and uniformly by graphene in the composite
Coated.Being not introduced into does not have the characteristic peak (10 degree or so) of graphite oxide in the N doping porous graphene sample of sulphur, only exist
The characteristic peak (23 degree and 43 degree) of graphene indicates the reduction ratio in water-heat process, and more thoroughly, sample purity is higher.
Fig. 2 is the data obtained by being tested by differential thermal analyzer, is shown by data in figure, sulphur/N doping porous graphite
The weight/mass percentage composition of sulphur about 76% in alkene composite, show that the specific surface area that the composite has is very big, loose structure
Substantially, it is fine to the covered effect of sulphur.
Fig. 3 is the micro-structure diagram shot by SEM, it can be seen that N doping porous graphite
Alkene has extremely abundant pore structure, and this has huge help for sulphur storage, and sulphur enters after pore structure it is difficult to be lost in so that
Lithium sulfur battery anode material prepared by the present invention has excellent cycle performance.
Fig. 4 is that electrode material prepared by this patent and lithium piece are assembled into coin shape test half-cell, and uses new prestige
The electrochemistry constant current charge-discharge curve of charge-discharge test instrument test, it may be seen that under 0.1C current densities, the head of the material
Secondary discharge capacity is up to 1537mAh/g, has a reaction platform in charging process, there is two reaction platforms, nothing in discharge process
Unnecessary side reaction platform also show the positive electrode has remarkable stable charge/discharge in cyclic process.
Embodiment 2：
The first step, prepare graphene oxide：
Prepare 5mg/mL graphene oxide water solution；
Second step, prepare N doping porous graphene：
It is 5mg/mL graphene oxide solutions A by concentration, a diameter of 200nm of concentration 30mg/mL, microballoon titanium dioxide
Silicon dispersion liquid B is 1 by liquor capacity ratio:2 are uniformly mixed to get mixed dispersion liquid C, and 0.35g ammonium hydrogen carbonate is added into 30m mixes
In dispersion liquid C, mixed dispersion liquid D is obtained, and ultrasonic disperse 2h is carried out to mixed dispersion liquid D using ultrasonic wave separating apparatus, is obtained
To the mixed uniformly suspension of graphene oxide-silica containing nitrogen source ammonium hydrogen carbonate, polytetrafluoroethylene (PTFE) has been placed it in
In the autoclave of liner, hydrothermal reduction 24 hours at 150 DEG C；The product that reaction obtains is washed with deionized laggard
Row vacuum drying treatment, the nitrogen-doped graphene-silicon dioxide composite material obtained after drying is put into mass percent concentration
To soak 12h in 20% hydrofluoric acid the silica spheres as template are etched away, that is, N doping porous graphite is made
Alkene sample；
3rd step, prepare sulphur/N doping porous graphene composite construction lithium sulfur battery anode material：
Porous nitrogen-doped graphene made from second step and pure phase nanometer sulphur powder are put into ball grinder, use planetary ball
Grinding machine mixed processing 5h, the mixture obtained after ball milling is put into the tube furnace under nitrogen protection, is heat-treated at 180 DEG C
12h, obtain sulphur/compound lithium sulfur battery anode material of porous nitrogen-doped graphene；
Wherein, the porous nitrogen-doped graphene of mass ratio：Pure phase nanometer sulphur powder=1: 3；
In described second step, ultrasonic disperse is ultrasonic wave separating apparatus, is carried out under 550W power.
In the 3rd described step, the rotating speed of planetary ball mill is 300rpm.
The flow of nitrogen is 200mL/min in the 3rd described step.
A kind of preparation method of above-mentioned lithium sulfur battery anode material, described graphene preparation process can use many existing
Known technology (such as hummers methods, solid phase/liquid phase are peeled off)；
A kind of preparation method of above-mentioned lithium sulfur battery anode material, involved raw material by commercially available, as
For the silica dispersions of the different-grain diameter of mould material to be commercially available, equipment used and technique are the technologies of the art
Known to personnel.
Unaccomplished matter of the present invention is known technology.
Claims (5)
- A kind of 1. preparation method of lithium sulfur battery anode material, it is characterized in that this method comprises the following stepsThe first step, prepare graphene oxide：Prepare 1~10mg/mL graphene oxide water solution；Second step, prepare N doping porous graphene：Solution A, solution B are mixed to get mixed dispersion liquid C, then ammonium hydrogencarbonate is added in mixed dispersion liquid C, is mixed Dispersion liquid D, and 1~5h of ultrasonic disperse is carried out to mixed dispersion liquid D using ultrasonic wave separating apparatus, obtain containing nitrogen source bicarbonate The mixed uniformly suspension of graphene oxide-silica of ammonia, place it in the autoclave of polytetrafluoroethyllining lining In, the hydrothermal reduction 6-24 hours at 100-200 DEG C；After the product that reaction obtains is washed with deionized, carries out vacuum and do Dry processing, obtained nitrogen-doped graphene-silicon dioxide composite material；Then 6~24h of immersion in hydrofluoric acid is put it into, i.e., N doping porous graphene is made；Wherein, solution A is that concentration is 1~10mg/mL graphene oxide solutions, solution B be concentration be 1~100mg/mL, microballoon A diameter of 10~300nm silica dispersions；Volume ratio is solution A：Solution B=1:1~3；Every 10~50mL mixing point 0.1~0.5g ammonium hydrogencarbonates are added in dispersion liquid C；3rd step, prepare sulphur/N doping porous graphene composite construction lithium sulfur battery anode material：Porous nitrogen-doped graphene made from second step and pure phase nanometer sulphur powder are put into ball grinder, use planetary ball mill 3~5h of mixed processing, the mixture obtained after ball milling is put into the tube furnace under nitrogen protection, at 100~200 DEG C at heat 8~24h is managed, obtains sulphur/compound lithium sulfur battery anode material of porous nitrogen-doped graphene；Wherein, the porous nitrogen-doped graphene of mass ratio：Pure phase nanometer sulphur powder=1: 3~10.
- 2. the preparation method of lithium sulfur battery anode material as claimed in claim 1, it is characterized in that in described second step, ultrasound Ultrasonic wave separating apparatus is separated into, is carried out under 300~650W power.
- 3. the preparation method of lithium sulfur battery anode material as claimed in claim 1, it is characterized in that in described second step, hydrogen fluorine Acid is that mass percent concentration is 5~40%.
- 4. the preparation method of lithium sulfur battery anode material as claimed in claim 1, it is characterized in that in the 3rd described step, planet The rotating speed of formula ball mill is 200~600rpm.
- 5. the preparation method of lithium sulfur battery anode material as claimed in claim 1, it is characterized in that nitrogen in the 3rd described step Flow be 100~250mL/min.
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