CN107093730A - Prelithiation tin base cathode material and preparation method and application - Google Patents
Prelithiation tin base cathode material and preparation method and application Download PDFInfo
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- CN107093730A CN107093730A CN201710316626.7A CN201710316626A CN107093730A CN 107093730 A CN107093730 A CN 107093730A CN 201710316626 A CN201710316626 A CN 201710316626A CN 107093730 A CN107093730 A CN 107093730A
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- prelithiation
- tin
- cathode material
- base cathode
- sncl
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000010406 cathode material Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002105 nanoparticle Substances 0.000 claims abstract description 26
- 229910001887 tin oxide Inorganic materials 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- 238000000576 coating method Methods 0.000 claims abstract description 23
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 16
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 15
- 239000008103 glucose Substances 0.000 claims abstract description 15
- 239000013078 crystal Substances 0.000 claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 13
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 12
- 229930006000 Sucrose Natural products 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000005720 sucrose Substances 0.000 claims abstract description 12
- 239000005864 Sulphur Substances 0.000 claims abstract description 11
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 8
- LTDAQVLIZRQEBW-UHFFFAOYSA-N [Li].[S].[Sn] Chemical compound [Li].[S].[Sn] LTDAQVLIZRQEBW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000003993 interaction Effects 0.000 claims abstract description 7
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims abstract description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims abstract description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 239000006229 carbon black Substances 0.000 claims description 10
- 239000011889 copper foil Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical compound [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 claims description 5
- 230000009977 dual effect Effects 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 3
- 238000001354 calcination Methods 0.000 abstract description 2
- 230000008014 freezing Effects 0.000 abstract 1
- 238000007710 freezing Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 125000004646 sulfenyl group Chemical group S(*)* 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- QRMHDYCPNIVCBO-UHFFFAOYSA-N [SH2]=N.[F] Chemical compound [SH2]=N.[F] QRMHDYCPNIVCBO-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- -1 sulfenyl lithium ion Chemical compound 0.000 description 2
- 239000010405 anode material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003738 black carbon Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of preparation method of prelithiation tin base cathode material, comprise the following steps:Take SnCl4·5H2O crystal or SnCl2It is dissolved in pure water, heating obtains the first mixed liquor, is cooled to room temperature;Add after glucose or sucrose, stirring and dissolving, heating obtains the second mixed liquor, is cooled to room temperature;It is then centrifuged for freezing, calcining obtains carbon coating tin oxide nano particles;It is constituted into galvanic cell with lithium piece, galvanic interaction is carried out and obtains prelithiation carbon coating tin oxide nano particles, i.e. prelithiation tin base cathode material.Above-mentioned prelithiation tin base cathode material directly can match to form the full battery of tin sulphur lithium ion with sulphur positive electrode;The present invention passes through carries out prelithiation to tin base cathode, it is to avoid to the lithiumation process of positive electrode, the obtained full battery of tin sulphur lithium ion possesses excellent cycle performance, high-energy-density, high rate capability and high service life.
Description
Technical field
The invention belongs to electrochmical power source technology, and in particular to a kind of prelithiation tin base cathode material and preparation method thereof is with answering
With.
Background technology
Due to the rise of mobile device and electric automobile and some other electrical equipment, energy storage device has been caused more
Carry out more concerns, and among this, because with the good cycle performance of high-energy-density, lithium battery has attracted science
Family greatly concern, this also results in the great development of lithium battery in recent years.However, as highly energy-consuming equipment is more and more, passing
The lithium ion battery of system has not caught up with the demand of people more and more, thus Large Copacity lithium ion battery increasingly by
Concern.Sulphur possesses the specific capacity for being up to 1672mAh g-1 as novel lithium battery positive electrode, at the same it is with low cost, it is one
Plant ideal anode material of lithium battery.But existing sulphur positive electrode is generally used in lithium metal battery as positive electrode
Use, and the practical application among lithium ion battery is then very limited, reason is that the property of lithium sulfide is highly unstable, and right
The lithiumation of sulphur is relatively difficult.Therefore, for lithium ion sulphur battery, the high-performance negative material exploitation that lithium is filled in advance seems outstanding
For key, technical barrier is still at present.
The content of the invention
In order to solve the problems of the prior art, the invention provides one kind suitable for tin sulphur lithium ion battery with sulfenyl
The tin base cathode material for the prelithiation that material positive pole is directly matched.
A kind of preparation method of prelithiation tin base cathode material of the present invention, comprises the following steps:
(1) SnCl is taken4·5H2O crystal or SnCl2It is dissolved in pure water, the obtained aqueous solution is heated to 90~230 DEG C,
Kept for 3~72 hours, obtain the first mixed liquor, be cooled to room temperature;
(2) glucose or sucrose are added in the first mixed liquor after being cooled down to step (1), after stirring, it is heated to 90~
230 DEG C are kept for 1~72 hour, are obtained the second mixed liquor, are cooled to room temperature;
(3) the second mixed liquor after step (2) is cooled down is centrifuged, and taking precipitate is freezed, and is subsequently placed in 300~900 DEG C, nitrogen
1-20h is calcined in gas or argon gas atmosphere, carbon coating tin oxide nano particles are obtained;
(4) carbon coating tin oxide nano particles obtained by step (3) are constituted into galvanic cell with lithium piece, carries out galvanic interaction
1-72 hours, obtain prelithiation carbon coating tin oxide nano particles, i.e. prelithiation tin base cathode material.
In step (1), the obtained aqueous solution refers to 0.1g~50g SnCl4·5H2O crystal or SnCl2It is dissolved in
Obtained in 10~200mL pure water.It is further preferred for 20~100mL pure water.
The first mixed liquor that step (1) is obtained is white stannic oxide nanometer crystalline deposit.
In step (2), the glucose or sucrose and SnCl of addition4·5H2O crystal or SnCl2Mass ratio be 0.5
~20:1.
It is further preferred that in step (2), the glucose or sucrose and SnCl of addition4·5H2O crystal or SnCl2
Mass ratio be 0.5~5:1.
In step (2), on the one hand stirring causes the glucose added or sucrose dissolving, on the other hand enables to step
(1) the stannic oxide nanometer crystallization obtained is uniformly scattered in solution.Second mixed liquor is nanoscale of the brown to black
Carbon coating stannic oxide particle dispersion liquid.
In step (3), gained carbon coating tin oxide nano particles particle diameter is 5~2000nm.
In step (3), centrifugal condition is 500~10000 revs/min, and lyophilisation condition is -5 DEG C~-60 DEG C processing.
In step (4), galvanic interaction is that, using electrolyte as mass transfer, the electrolyte is dissolved in carbonic acid including lithium hexafluoro phosphate
The electrolyte or organic electrolyte of ester, such as double fluorine sulfimide base lithium electrolyte.
Gained prelithiation tin base cathode material is prepared according to above-mentioned preparation method also in protection scope of the present invention.
Above-mentioned prelithiation tin base cathode material in tin sulphur lithium ion battery as negative pole application.
The application comprises the following steps:Weigh prelithiation tin base cathode material, Kynoar (PVDF) and super phosphorus
Carbon black (Super P carbon black), is scattered in after mixing in 1-METHYLPYRROLIDONE (NMP), and stirring makes Kynoar
(PVDF) dissolve, and be well mixed other materials, be then coated on 2-20 microns of thick dual light copper foils, obtain negative pole copper
Paillon foil, directly matches to form the full battery of tin sulphur lithium ion after cutting with sulphur positive electrode.
The mass ratio of the prelithiation tin base cathode material, Kynoar and super phosphorus carbon black is (70~100):(1~
20):(1~20).
The mass volume ratio of the Kynoar (PVDF) and 1-METHYLPYRROLIDONE (NMP) is 0.5~100mg/ml.
Preferably 10~50mg/ml.
Unaccounted content is that can be achieved all in accordance with industry routine operation in technical solution of the present invention.
Beneficial effect:A kind of negative pole prelithiation tin base cathode material that can be matched with sulphur positive pole of the present invention and its preparation side
Method, by carrying out prelithiation to negative pole, it is to avoid to the lithiumation process of positive electrode so that the composition of sulfenyl lithium ion battery is not
It is difficult again;And using the prelithiation tin base cathode material and sulfur-based positive electrode match materials into the full battery of tin sulphur lithium ion gather around
There are excellent cycle performance, high-energy-density, high rate capability and high service life.
Embodiment
The present invention is explained in detail with reference to specific embodiment.
Reagent source:Super phosphorus carbon black (Super P carbon black) is purchased from Te Migao graphite Co., Ltd of Switzerland.
Other reagents not explained are the commercially available gained in market.
The preparation of the prelithiation tin base cathode material of embodiment 1
Comprise the following steps:
(1) 0.5g SnCl accurately are weighed4·5H2O crystal, is dissolved in 20mL pure water, is transferred in reactor, at 90 DEG C
Heating 3 hours, obtains the first mixed liquor, and taking-up is cooled to room temperature;
(2) it is accurate to weigh in 1g glucose or sucrose the first mixed liquor of addition, it is dissolved in wherein, and stirring makes wherein to have obtained
To tin oxide nano particles being scattered in solution well, after glucose is completely dissolved, then be placed in reactor,
In being heated 1 hour at 100 DEG C, the second mixed liquor is obtained, taking-up is cooled to room temperature;
(3) the second mixed liquor after step (2) is cooled down is with 1000 revs/min of centrifugations, and taking precipitate is lyophilized at -60 DEG C,
The brown or black powder of the carbon coating tin oxide nano particles containing functional group are obtained, is placed at a temperature of 400 DEG C, nitrogen gas
Calcined in atmosphere 1 hour and obtain carbon coating tin oxide nano particles;
(4) carbon coating tin oxide nano particles obtained by step (3) are constituted into galvanic cell with lithium piece, with double fluorine sulfimides
Base lithium electrolyte is mass transfer, and the galvanic interaction carried out 1 hour is that can obtain prelithiation carbon coating tin oxide nano particles, i.e.,
Prelithiation tin base cathode material.
Application of the prelithiation carbon bag tin ash of embodiment 2 in sulfenyl lithium battery
Using 1:The prelithiation carbon bag tin oxide nano particles that 160mg embodiments 1 are prepared accurately are weighed,
20mgPVDF, 20mg Super P carbon black, are scattered in 2mLNMP (1-METHYLPYRROLIDONE), and stirring makes PVDF molten
Solve and be well mixed other materials, be coated on afterwards on 9 microns thick dual light copper foil, obtain required negative copper foil piece,
It is used directly to match into the full battery of sulfenyl with sulphur positive electrode after cutting.
Using 2:The prelithiation carbon bag tin oxide nano particles that 180mg embodiments 1 are prepared accurately are weighed,
10mgPVDF, 10mg Super P carbon black, being scattered in 10mLNMP stirrings dissolves PVDF and mixes other materials
Close uniform, be coated on afterwards on 5 microns thick dual light copper foils, obtain required negative copper foil piece, be used directly to after cutting with
Sulphur positive electrode matches into the full battery of sulfenyl.
Using 3:It is accurate to weigh the prelithiation carbon bag tin oxide nano particles that 190mg embodiments 1 are prepared, 6mgPVDF,
4mg Super P carbon black, are scattered in 0.3mL NMP, and stirring dissolves PVDF and is well mixed other materials,
It is coated on afterwards on 18 microns thick dual light copper foil, obtains required negative copper foil piece, be used directly to after cutting and sulphur positive pole
Match materials are into the full battery of sulfenyl.
The tin sulphur battery prepared using battery test system to embodiment 2 carries out performance detection.It the results are shown in Table 1.
Table 1
Embodiment 3
The preparation of prelithiation tin base cathode material, comprises the following steps:
(1) 0.1g SnCl accurately are weighed4·5H2O crystal, is dissolved in 50mL pure water, is transferred in reactor, at 220 DEG C
Lower heating 60 hours, obtains the first mixed liquor, and taking-up is cooled to room temperature;
(2) it is accurate to weigh in 2g glucose or sucrose the first mixed liquor of addition, it is dissolved in wherein, and stirring makes wherein to have obtained
To tin oxide nano particles being scattered in solution well, after glucose is completely dissolved, then be placed in reactor,
Heated 10 hours at 100 DEG C, obtain the second mixed liquor, taking-up is cooled to room temperature;
(3) the second mixed liquor after step (2) is cooled down is with 800 revs/min of centrifugations, and taking precipitate is lyophilized at -30 DEG C, i.e.,
The brown or black powder of the carbon coating tin oxide nano particles containing functional group are obtained, is placed at a temperature of 800 DEG C, nitrogen atmosphere
Middle calcining obtains carbon coating tin oxide nano particles in 20 hours;
(4) carbon coating tin oxide nano particles obtained by step (3) and lithium piece are constituted into galvanic cell, it is molten with lithium hexafluoro phosphate
It is mass transfer in the electrolyte of carbonic ester, the galvanic interaction carried out 10 hours is that can obtain prelithiation carbon coating stannic oxide nanometer
Particle, i.e. prelithiation tin base cathode material.
Embodiment 4
The preparation of prelithiation tin base cathode material, comprises the following steps:
(1) 50g SnCl accurately are weighed4·5H2O crystal, is dissolved in 200mL pure water, is transferred in reactor, at 150 DEG C
Lower heating 10 hours, obtains the first mixed liquor, and taking-up is cooled to room temperature;
(2) it is accurate to weigh in 25g glucose or sucrose the first mixed liquor of addition, it is dissolved in wherein, and stirring makes wherein
Obtained tin oxide nano particles being scattered in solution well, after glucose is completely dissolved, then is placed on reactor
In, heated 5 hours at 200 DEG C, obtain the second mixed liquor, taking-up is cooled to room temperature;
(3) the second mixed liquor after step (2) is cooled down is with 2000 revs/min of centrifugations, and taking precipitate is lyophilized at -10 DEG C,
The brown or black powder of the carbon coating tin oxide nano particles containing functional group are obtained, is placed at a temperature of 900 DEG C, argon gas gas
Calcined in atmosphere 20 hours and obtain carbon coating tin oxide nano particles;
(4) carbon coating tin oxide nano particles obtained by step (3) are constituted into galvanic cell with lithium piece, with double fluorine sulfimides
Base lithium electrolyte is mass transfer, and the galvanic interaction carried out 3 hours is that can obtain prelithiation carbon coating tin oxide nano particles, i.e.,
Prelithiation tin base cathode material.
Embodiment 5
The preparation of prelithiation tin base cathode material, preparation manipulation be the same as Example 1, difference is:
In step (1), 10g SnCl are weighed4·5H2O crystal, is dissolved in 50mL pure water;
In step (2), accurately weigh 50g glucose or sucrose is added in the first mixed liquor.
Embodiment 6
The preparation of prelithiation tin base cathode material, preparation manipulation be the same as Example 1, difference is:
In step (1), 0.8g SnCl are weighed4·5H2O crystal, is dissolved in 50mL pure water;
In step (2), accurately weigh 8g glucose or sucrose is added in the first mixed liquor.
Claims (10)
1. a kind of preparation method of prelithiation tin base cathode material, it is characterised in that comprise the following steps:
(1) SnCl is taken4·5H2O crystal or SnCl2It is dissolved in pure water, the obtained aqueous solution is heated to 90~230 DEG C, holding
3~72 hours, the first mixed liquor is obtained, room temperature is cooled to;
(2) added in the first mixed liquor after being cooled down to step (1) after glucose or sucrose, stirring and dissolving, it is heated to 90~
230 DEG C are kept for 1~72 hour, are obtained the second mixed liquor, are cooled to room temperature;
(3) the second mixed liquor after step (2) is cooled down is centrifuged, and taking precipitate is freezed, and is subsequently placed in 300~900 DEG C, nitrogen or
1-20h is calcined in person's argon gas atmosphere, carbon coating tin oxide nano particles are obtained;
(4) carbon coating tin oxide nano particles obtained by step (3) are constituted into galvanic cell with lithium piece, carries out galvanic interaction 1-72
Hour, obtain prelithiation carbon coating tin oxide nano particles, i.e. prelithiation tin base cathode material.
2. preparation method according to claim 1, it is characterised in that in step (1), the obtained aqueous solution refer to by
0.1g~50g SnCl4·5H2O crystal or SnCl2It is dissolved in 10~200mL pure water.
3. preparation method according to claim 1, it is characterised in that in step (2), the glucose or sucrose of addition with
SnCl4·5H2O crystal or SnCl2Mass ratio be 0.5~20:1.
4. preparation method according to claim 1, it is characterised in that in step (3), gained carbon coating stannic oxide nanometer
Grain diameter is 5~2000nm.
5. preparation method according to claim 1, it is characterised in that in step (3), centrifugal condition is 500~10000
Rev/min, lyophilisation condition is -5 DEG C~-60 DEG C.
6. gained prelithiation tin base cathode material is prepared according to any preparation method in claim 1-5.
7. prelithiation tin base cathode material described in claim 5 makees the application of negative pole in tin sulphur lithium ion battery.
8. application according to claim 6, it is characterised in that comprise the following steps:Weigh prelithiation tin base cathode material,
Kynoar and super phosphorus carbon black, are scattered in 1-METHYLPYRROLIDONE after mixing, and stirring dissolves Kynoar, and makes
Other materials is well mixed, and is then coated on 2-20 microns of thick dual light copper foils, is obtained negative copper foil piece, after cutting directly
Match to form the full battery of tin sulphur lithium ion with sulphur positive electrode.
9. application according to claim 8, it is characterised in that the prelithiation tin base cathode material, PVDF polyvinylidene fluorides
The mass ratio of alkene and super phosphorus carbon black is (70~100):(1~20):(1~20).
10. application according to claim 8, it is characterised in that the matter of the Kynoar and 1-METHYLPYRROLIDONE
Amount volume ratio is 0.5~100mg/ml.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109378464A (en) * | 2018-12-04 | 2019-02-22 | 南京大学 | A kind of stannic oxide carbon nano-complex and the preparation method and application thereof |
CN111540891A (en) * | 2020-05-11 | 2020-08-14 | 中国科学院重庆绿色智能技术研究院 | Preparation method of low-cost high-performance tin-carbon lithium battery negative electrode material |
CN112490429A (en) * | 2020-12-03 | 2021-03-12 | 上海汉行科技有限公司 | Carbon-coated tin dioxide and tin diselenide composite material and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101823760A (en) * | 2010-05-13 | 2010-09-08 | 西安交通大学 | Method for preparing nanometer foam stannic oxide of lithium ion battery cathode material |
CN104538591A (en) * | 2014-12-30 | 2015-04-22 | 天津巴莫科技股份有限公司 | Pre-lithiation method of lithium ion battery negative electrode material |
CN104956521A (en) * | 2012-12-19 | 2015-09-30 | 亿目朗美国股份有限公司 | Negative electrode active material for energy storage |
CN105845894A (en) * | 2016-05-04 | 2016-08-10 | 合肥国轩高科动力能源有限公司 | Pre-lithiation method and device for negative pole pieces of lithium-ion battery |
-
2017
- 2017-05-08 CN CN201710316626.7A patent/CN107093730B/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101823760A (en) * | 2010-05-13 | 2010-09-08 | 西安交通大学 | Method for preparing nanometer foam stannic oxide of lithium ion battery cathode material |
CN104956521A (en) * | 2012-12-19 | 2015-09-30 | 亿目朗美国股份有限公司 | Negative electrode active material for energy storage |
CN104538591A (en) * | 2014-12-30 | 2015-04-22 | 天津巴莫科技股份有限公司 | Pre-lithiation method of lithium ion battery negative electrode material |
CN105845894A (en) * | 2016-05-04 | 2016-08-10 | 合肥国轩高科动力能源有限公司 | Pre-lithiation method and device for negative pole pieces of lithium-ion battery |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109378464A (en) * | 2018-12-04 | 2019-02-22 | 南京大学 | A kind of stannic oxide carbon nano-complex and the preparation method and application thereof |
CN109378464B (en) * | 2018-12-04 | 2022-06-14 | 南京大学 | Tin dioxide carbon nano composite and preparation method and application thereof |
CN111540891A (en) * | 2020-05-11 | 2020-08-14 | 中国科学院重庆绿色智能技术研究院 | Preparation method of low-cost high-performance tin-carbon lithium battery negative electrode material |
CN112490429A (en) * | 2020-12-03 | 2021-03-12 | 上海汉行科技有限公司 | Carbon-coated tin dioxide and tin diselenide composite material and preparation method thereof |
CN112490429B (en) * | 2020-12-03 | 2023-06-13 | 上海汉行科技有限公司 | Carbon-coated tin dioxide and tin diselenide composite material and preparation method thereof |
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