CN107275571A - A kind of full battery of lithium sulfide/nano-silicone wire/carbon and preparation method and application - Google Patents
A kind of full battery of lithium sulfide/nano-silicone wire/carbon and preparation method and application Download PDFInfo
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- CN107275571A CN107275571A CN201710712065.2A CN201710712065A CN107275571A CN 107275571 A CN107275571 A CN 107275571A CN 201710712065 A CN201710712065 A CN 201710712065A CN 107275571 A CN107275571 A CN 107275571A
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- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- 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
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on 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
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a kind of full battery of lithium sulfide/nano-silicone wire/carbon and preparation method and application.The preparation method is comprised the following steps：Lithium sulfate is distributed in water, then organic carbon source is distributed in polar organic solvent, drying-granulating prepares composite precursor after both are well mixed, and then high-temperature calcination obtains carbon coating lithium sulfide composite positive pole；Nano-silicon, organic carbon source and Delanium are distributed in organic solvent respectively, then by the well mixed rear drying-granulating of three, high-temperature calcination obtains carbon coating silicon-carbon composite cathode material；Finally carbon coating lithium sulfide composite positive pole and carbon coating silicon-carbon composite cathode material are assembled, the full battery of lithium sulfide/nano-silicone wire/carbon is obtained.The preparation technology of the present invention is simple, it is easy to operate, it is adapted to large-scale production, and obtained full battery has the advantages that first charge-discharge efficiency is high, specific capacity is high, good cycle, the demand of high power capacity electronic equipment can be met, it is adaptable to electric automobile or portable type electronic product.
Description
Technical field
The invention belongs to energy new material technology field, more particularly to a kind of full battery of lithium sulfide/nano-silicone wire/carbon and its system
Preparation Method and application.
Background technology
Lithium ion battery technology is considered as one of optimal green energy resource storage and switch technology.With ni-mh, nickel chromium triangle
Compared Deng secondary cell, lithium ion battery has the advantages that long-life, high-energy-density, do not have memory effect, is answered extensively
For portable electric appts, among communication apparatus, and electric automobile market.Wherein, the choosing of positive electrode and negative material
Select and vital effect is played to performance of lithium ion battery.
Positive pole material using lithium-sulphur as lithium ion battery is one of focus of high-capacity lithium ion cell research in recent years.
Compared with conventional lithium ion battery technology, lithium-sulfur cell in terms of specific capacity, energy density and power density have it is only
Thick advantage.In addition, lithium-sulfur cell also has, electrode material abundance, cost be low, environmentally friendly, battery security is good
The advantages of.The theoretical specific capacity of Lithium-sulphur battery anode material lithium sulfide is 1160mA h/g, using the teaching of the invention it is possible to provide about 2V electric discharge is put down
Platform.Using elemental sulfur as positive electrode, it can be matched with general negative electrode of lithium ion battery, but prelithiation trouble, system
It is standby complicated.
The selection of negative material is also most important with preparing.There is relatively low theoretical appearance in the graphite cathode material used at present
Measure (372mA h/g), and the room for promotion very little of its capacity, far from the Times ' Demand for meeting high-capacity lithium ion cell.Separately
Outside, silica-base material is the more novel anode material of Recent study.Simple substance silicon materials are because with high theoretical specific capacity
(4200mA h/g) and receive much concern.But huge Volumetric expansion is shown during Li insertion extraction so that material structure
Destruction is subject to, and then causes efficiency first and stable circulation performance poor.Above mentioned problem is tackled, conventional means are to enter silicon
Row nanosizing, alloying and Composite, but its complex process, the battery prepared have that irreversible capacity is big, electric conductivity
The problem of energy difference and poor cyclical stability.Therefore it provides a kind of preparation technology is simple, easy to operate, and first charge-discharge efficiency
High, specific capacity is high, the full battery process of good cycle is significant.
The content of the invention
The primary and foremost purpose of the present invention is to overcome the shortcoming and deficiency of prior art, and there is provided a kind of lithium sulfide/nano-silicone wire/carbon
The preparation method of full battery.
Another object of the present invention is to provide the full battery of lithium sulfide/nano-silicone wire/carbon that methods described is prepared.
A further object of the present invention is the application for providing the full battery of lithium sulfide/nano-silicone wire/carbon.
The purpose of the present invention is achieved through the following technical solutions：A kind of preparation method of the full battery of lithium sulfide/nano-silicone wire/carbon,
Comprise the following steps：
(1) lithium sulfate is distributed in water, obtains solution A, organic carbon source is distributed in polar organic solvent, obtain molten
Liquid B, then solution A and solution B are well mixed, obtain mixed solution C；
(2) powder processed is dried in the mixed solution C obtained in step (1), obtains presoma D；
(3) the presoma D obtained in step (2) is calcined, obtains carbon coating lithium sulfide composite positive pole E；
(4) nano-silicon is distributed in organic solvent, obtains suspension F, organic carbon source is distributed in organic solvent, obtain
To solution G, Delanium is distributed in organic solvent, suspension H is obtained, then suspension F, solution G and suspension H are mixed
Uniformly, mixed liquor I is obtained；
(5) powder processed is dried in the mixed liquor I obtained in step (4), obtains presoma J；
(6) the presoma J obtained in step (5) is calcined, obtains carbon coating silicon-carbon composite cathode material K；
(7) it is the carbon coating lithium sulfide composite positive pole E, binding agent and the conductive agent that are obtained in step (3) is well mixed
After be tuned into slurry, be coated with aluminium foil, dry, roll-in obtains lithium-sulfur cell positive plate；
(8) after the carbon coating silicon-carbon composite cathode material K, binding agent and the conductive agent that are obtained in step (6) being well mixed
Slurry is tuned into, is coated with aluminium foil, is dried, roll-in obtains lithium-sulfur cell negative plate；
(9) lithium-sulphur that will be obtained in the lithium-sulfur cell positive plate obtained in step (7), barrier film, electrolyte and step (8)
Battery cathode sheet is packaged, and obtains the full battery of lithium sulfide/nano-silicone wire/carbon.
Water described in step (1) is preferably deionized water.
Polar organic solvent described in step (1) is water or tetrahydrofuran.
Described water is preferably deionized water.
Organic carbon source described in step (1) is long-chain organic carbon source；Preferably sucrose, glucose, pitch and polyethylene
At least one of alcohol.
Described polyvinyl alcohol is preferably the polyvinyl alcohol of molecular weight 20000.
The mass ratio of lithium sulfate and organic carbon source described in step (1) is preferably 1：(7.0~7.5).
Described in step (1) it is scattered be preferably using stir by the way of disperseed.
The condition of described stirring is：400~2000r/min stirs 0.5~2h；The condition of stirring is preferably：1500r/
Min stirs 0.5~1h.
Drying described in step (2) is preferably to be dried using closed cycle spray drying machine.
Described closed cycle spray drying machine is centrifugal atomizer, and its rotating speed is 15000~40000r/min, is imported and exported
Temperature is respectively 100~300 DEG C and 60~120 DEG C, and charging rate is 10~20mL/min.
Calcining described in step (3) and step (6) is preferably to be calcined under inert gas shielding.
Described inert gas is preferably nitrogen or argon gas；The nitrogen or purity that more preferably purity is 99.99% is
99.999% argon gas.
The condition of calcining described in step (3) is：600~850 DEG C are warming up to 2~10 DEG C/min speed, then it is permanent
Temperature keeps 1~5h；The condition of calcining is preferably：700~750 DEG C are warming up to 5 DEG C/min speed, then constant temperature keeps 3~4h.
The particle size of nano-silicon described in step (4) is preferably 30~100nm.
The dispersing mode of nano-silicon is preferably ultrasonic disperse described in step (4).
Described ultrasonic power is preferably 300W.
The described ultrasonic time is preferably 10~40min.
The dispersing mode of organic carbon source and Delanium described in step (4) is preferably dispersed with stirring.
The condition of described stirring is preferably：400~2000r/min stirs 0.5~2h.
The solid content of suspension F and suspension H described in step (4) are all 20~35%.
Organic solvent described in step (4) is preferably one kind in absolute ethyl alcohol, acetone and tetrahydrofuran.
During organic carbon source described in step (4) is preferably citric acid, CMC (carboxymethyl cellulose), pitch and glucose
At least one.
The mass ratio of nano-silicon, organic carbon source and Delanium described in step (4) is 1：(2~4)：(0.5~
0.8)。
It is well mixed to be well mixed by the way of stirring described in step (4).
The condition of described stirring is preferably that 400~2000r/min stirs 1~5h.
Drying described in step (5) is to be dried in drying box；Done preferably in 60~90 DEG C of drying box
Dry 6~14h.
Powder processed described in step (5) is preferably to carry out powder processed by the way of grinding.
The condition of calcining described in step (6) is：700~900 DEG C, then constant temperature are warming up to 2~5 DEG C/min speed
Keep 3~10h.
The mass ratio of carbon coating lithium sulfide composite positive pole E, binding agent and conductive agent described in step (7) are (70
~84)：(15~8)：(15~8)；Mass ratio is preferably 8：1：1.
Binding agent described in step (7) is preferably polyvinylidene fluoride (PVDF) or PVP K30 (PVP-
K30)。
Conductive agent described in step (7) is preferably conductive carbon black Super-P, Ketjen black or acetylene black.
The thickness of coating described in step (7) is preferably 120~200 microns.
Drying described in step (7) and step (8) is vacuum drying；Preferably under 50~100 DEG C of vacuum condition
Dry 5~24h.
The thickness of roll-in described in step (7) is preferably 90~140 microns.
Aluminium foil described in step (7) and step (8) is preferably the aluminium foil that thickness is 10 μm.
The slurry that is tuned into described in step (7) and step (8) is tuned into slurry to add solvent.
Described solvent is preferably 1-METHYLPYRROLIDONE or dimethylformamide.
The consumption of described solvent is 1 by the mass ratio of solute and solvent:2 proportionings are calculated, wherein, solute is multiple for lithium sulfide
Close positive electrode E (or silicon-carbon composite cathode material K), binding agent and conductive agent.
Carbon coating silicon-carbon composite cathode material K, binding agent described in step (8) and the mass ratio of conductive agent mixing are
(76~84)：(12~8)：(12~8)；Mass ratio is preferably 8：1：1.
Binding agent described in step (8) is preferably the binding agent LA132 of Chengdu Yin Dile companies.
Conductive agent described in step (8) is conventional commercial electroconductive liquid purchased in market；Preferably conductive carbon black Super-P.
The thickness of coating described in step (8) is preferably 100~180 microns.
The thickness of roll-in described in step (8) is preferably 75~150 microns.
Barrier film described in step (9) is conventional lithium ion battery separator purchased in market.
Electrolyte described in step (9) is conventional lithium-sulfur cell electrolyte purchased in market.
A kind of full battery of lithium sulfide/nano-silicone wire/carbon, is prepared by the method described in any of the above-described.
The described full battery of lithium sulfide/nano-silicone wire/carbon, in addition to anode cover, pad and negative electrode casing, by anode cover, positive pole
Piece, electrolyte, barrier film, negative plate, pad and negative electrode casing are assembled and sealed in order.
Application of the described full battery of lithium sulfide/nano-silicone wire/carbon in electric automobile or portable type electronic product, lithium sulfide/
The full battery of nano-silicone wire/carbon not only conforms with requirement of the electric automobile to electrokinetic cell, also meets portable type electronic product to electrochmical power source
Lightweight, miniaturization, inexpensive and nontoxic requirement.
The principle of the present invention：
The present invention provides a kind of preparation method and both positive and negative polarity matching technique of the full battery material of high-performance lithium-sulphur.By dry
Dry granulation, the method for high-temperature calcination prepare the vulcanization lithium anode material of carbon coating；Pass through bonding by carrier of Delanium
Dry, high-temperature calcination obtains silicon-carbon composite cathode material.Prepared by the present invention and packaging technology step is concise, easy to operate, made
Standby material can be used without purifying and prelithiation processing directly as lithium-sulfur cell electrode active material.For lithium-sulphur electricity
Chi Zhong, material has that lithium storage content is big, the excellent feature of high rate performance, meets high performance lithium ion battery electrode activity material of new generation
The requirement of material.
Positive pole vulcanizes the preparation of lithium material, and using closed cycle spray drying machine, composite precursor is obtained first, is made organic
Carbon source is evenly dispersed in lithium sulfate surface, and rear high temperature makes lithium sulfate and carbon source thermally decompose altogether for lithium sulfide, obtains carbon coating
Vulcanize lithium anode material.The preparation of vulcanization lithium carries out reaction using lithium metal and elemental sulfur and produced, and cost is high and needs place
Impurities phase is managed, to solve the above problems, the present invention, which provides a kind of reducing process of high-efficient simple, prepares lithium sulfate, the method can have
Effect reduces cost, and reduction dephasign is conductive carbon, has facilitation to material property lifting, thus need not remove the place of dephasign
Reason, eliminates associated process steps.In terms of negative pole silica-base material, agglomeration due to nano-silicon and its easily is produced, so as to draw
The less efficient first of lithium cell cathode material is played, the poor shortcoming of cycle performance, conventional mode can not allow nano-silicon very
It is dispersed in graphite surface well and forms core shell structure.Cell powder is used for the technical deficiency present invention that solves the problems, such as above-mentioned
It (is determining electrode wherein by the dispersed of nano-silicon that broken machine, which carries out ultrasound to make nano-silicon be evenly dispersed in Delanium surface,
The key of material electrochemical performance).By electro-chemical test, positive electrode and silicon-carbon cathode material are used as by the lithium sulfide of carbon coating
Expect that the full battery first charge-discharge efficiency that is assembled into is high, specific capacity is high, good cycle, first specific capacity up to 800mAh/g with
On.
The present invention has the following advantages and effect relative to prior art：
(1) positive electrode of the present invention takes full advantage of closed cycle spray drying machine and prepares composite precursor, makes organic carbon
Source is evenly dispersed in lithium sulfate surface, and high-temperature process makes lithium sulfate pyrolysis be lithium sulfide, makes full use of reactant, step letter
It is single, save the links such as removal of impurities.
(2) negative material of the present invention successfully solves silica-base material in the prior art and is actually preparing answering for cathode of lithium battery
Used time, the irreversible capacity loss that exists is big, poor electric conductivity and the problem of poor cyclical stability.
(3) positive and negative electrode material primary particle particle diameter produced by the present invention is smaller, shows that chemical property is outstanding, specific volume
Amount is high, the advantage of good cycling stability.
(4) the full battery of lithium sulphur prepared by the present invention has first charge-discharge efficiency height, specific capacity high, good cycle
Advantage, is adapted to the demand of high power capacity electronic equipment, makes the application of lithium battery wider.
(5) ingredient requirement of the present invention is low, preparation technology is few, process is simple, easy to operate, and suitable large-scale production is used.System
Standby material is applied to lithium-sulfur cell, with lithium storage content is big, the excellent feature of high rate performance, meet high-performance lithium of new generation from
The requirement of sub- battery active material.
(6) present invention containing lithium, the compound of sulphur and long-chain organic carbon source to be used as lithium sulfide positive electrode material precursor, high temperature
Calcining obtains lithium sulfide compound, the problem of solving lithium-sulfur cell prelithiation；Negative material is then using the compound of silicon and graphite
Thing, the compound can provide the specific capacity far above graphite cathode.The full battery of lithium-sulphur, initial charge ratio are assembled into by above-mentioned
Capacity reaches more than 800mAh/g, solves the problem of existing lithium ion battery specific capacity is low, energy density is low.
Brief description of the drawings
Fig. 1 is the XRD spectrogram of the vulcanization lithium anode material of carbon coating made from embodiment 1.
Fig. 2 is the XRD spectrogram of silicon-carbon composite cathode material made from embodiment 1.
Fig. 3 schemes for the SEM of the vulcanization lithium anode material of carbon coating made from embodiment 2.
Fig. 4 schemes for the SEM of silicon-carbon composite cathode material made from embodiment 2.
Fig. 5 is the cyclic voltammetry curve figure first of the vulcanization lithium anode material of carbon coating made from embodiment 3.
The silicon-carbon Compound Negative that Fig. 6 is the vulcanization lithium anode material of carbon coating made from embodiment 3 and Delanium is carrier
The first charge-discharge curve map for the full battery that pole material is assembled into.
Embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Unless otherwise noted, all raw materials and medicament in the present invention are the raw material of conventional market, reagent.
Embodiment 1
(1) carbon coating vulcanizes the preparation of lithium anode material, comprises the following steps that：
(1) 16.7g lithium sulfates are scattered in 200mL deionized waters, 1500r/min high-speed stirred 0.5h obtain solution
A；
(2) 125g sucrose is dissolved in 200mL deionized waters, 1500r/min high-speed stirred 0.5h obtain mixed solution
B；
(3) solution A made from step (1) is added in solution B made from step (2), be well mixed, obtain mixing molten
Liquid C, then carries out closed cycle spray by mixed liquor C and dries powder processed, obtain presoma D；Wherein, closed cycle spray dries system
The rotating speed of centrifugal atomizer is 20000r/min during powder, and out temperature is respectively 200 DEG C and 100 DEG C, and charging rate is 15mL/
min；
(4) presoma D made from step (3) is placed in tube furnace, is passed through the nitrogen that purity is 99.99%, and with 5
DEG C/min speed reacts 3h after being warming up to 700 DEG C, obtains carbon coating vulcanization lithium anode material.
(2) Delanium is the preparation of the silicon-carbon composite cathode material of carrier, is comprised the following steps that：
(1) 12.8g nano-silicons (particle diameter is 30~100nm) are scattered in 150mL absolute ethyl alcohols, in cell pulverization ultrasound
Ultrasound 10min (power 300W), obtains suspension A in machine；
(2) 25.6g glucose is added in 150mL absolute ethyl alcohols, 1000r/min high-speed stirred 1h obtain solution B；
(3) 9.0g Delaniums are added in 150mL absolute ethyl alcohols, and 1500r/min high-speed stirred 2h, obtain suspended
Liquid C；
(4) solution B made from suspension A made from step (1) and step (2) is added to suspended made from step (3)
In liquid C, 1000r/min high-speed stirred 1h obtain mixed liquor D；Then mixed liquor D is dried in drying box, temperature is 80 DEG C,
Time is 12h, and grinds powder-grinding with Portland is ground, and obtains presoma E；
(5) presoma E made from step (4) is placed in tube furnace, is passed through the nitrogen that purity is 99.99%, and with 2
DEG C/min speed reacts 6h after being warming up to 700 DEG C, obtains the lithium ion battery silicon-carbon composite negative pole using Delanium as carrier
Material.
(3) lithium anode material will be vulcanized made from step (1) and carries out XRD spectrum detection, testing result is as shown in Figure 1.
It can be seen from figure 1 that the diffraction maximum of lithium sulfide has been rendered obvious by collection of illustrative plates, the peak and standard PDF cards (JCPDS NO.23-
0369) fit like a glove.Lithium sulfide reacts the impurity produced with vapor when detection is in the peak of the lithium hydroxide produced in Fig. 1.Step
Suddenly silicon-carbon composite cathode material made from (two) carries out XRD spectrum detection, and testing result is as shown in Figure 2.As can be seen from Figure 2,
The diffraction maximum and standard PDF cards (JCPDS of the diffraction maximum superposition of graphite and silicon, graphite and silicon have been rendered obvious by collection of illustrative plates
NO.021-0212 and JCPDS NO.027-1402) fit like a glove, show that the two belongs to that physics is compound not to chemically react
New thing phase is produced, particularly inactive SiC materials are not formed, probably occurs one at 23 ° between 15 °~35 ° in addition
Steamed bun peak, peak correspondence amorphous state amorphous carbon peak.
(4) prepared by battery electrode piece, comprises the following steps that：
(1) carbon coating for preparing step (1) vulcanizes lithium anode material, binding agent polyvinylidene fluoride and conductive carbon black
Super-P (conductive agent) is according to mass ratio 8:1:1 mixing, using 1-METHYLPYRROLIDONE as the solvent (mass ratio of solute and solvent
For：1:2) slurry is tuned into, (coating thickness is 100 μm) is coated on the aluminium foil of 10 μ m-thicks, and through vacuum 80 DEG C of dry 10h, roller
Pressure (thickness of roll-in for 85 μm).It is prepared into lithium-sulfur cell positive plate 1；
(2) silicon-carbon composite cathode material for preparing step (2), binding agent LA132 (Chengdu Yin Dile companies, binding agent
Solids content is 15%) and conductive carbon black Super-P is according to weight ratio 8:1:1 uniform mixing, using deionized water as solvent (solute
Mass ratio with solvent is：1:2) slurry is tuned into, is coated on copper foil, coating thickness is 100 μm, and through 100 DEG C of dryings of vacuum
10h, roll-in (roll-in thickness is 85 μm), are prepared into lithium-sulfur cell negative plate 1.
(5) assembling of the full battery of lithium-sulphur, is comprised the following steps that：
Under normal temperature condition, by CR2032 anode covers, lithium-sulfur cell positive plate 1, electrolyte, barrier film, lithium-sulfur cell negative pole
Piece 1, pad and CR2032 negative electrode casings are assembled and sealed in order, obtain the full battery of lithium sulfide/nano-silicone wire/carbon.
Embodiment 2
(1) carbon coating vulcanizes the preparation of lithium anode material, comprises the following steps that：
(1) 16.7g lithium sulfates are scattered in 200mL deionized waters, 1500r/min high-speed stirred 0.5h obtain solution
A；
(2) 120g pitches are dissolved in 200mL tetrahydrofurans, 1500r/min high-speed stirred 1h obtain mixed solution B；
(3) solution A made from step (1) is added in solution B made from step (2) and be well mixed, obtain mixing molten
Liquid C, then carries out closed cycle spray by mixed liquor C and dries powder processed, obtain presoma D；Wherein, closed cycle spray dries system
The rotating speed of centrifugal atomizer is 20000r/min during powder, and out temperature is respectively 220 DEG C and 100 DEG C, and charging rate is 15mL/
min；
(4) presoma D made from step (3) is placed in tube furnace, be passed through purity be 99.99% nitrogen and with 5 DEG C/
Min speed reacts 4h after being warming up to 750 DEG C, obtains carbon coating vulcanization lithium anode material.
(2) Delanium is the preparation of the silicon-carbon composite cathode material of carrier, is comprised the following steps that：
(1) 12.8g nano-silicons (particle diameter is 30~100nm) are scattered in 150mL absolute ethyl alcohols, in cell pulverization ultrasound
Ultrasound 20min (power 300W), obtains suspension A in machine；
(2) 51.2g CMC (carboxymethyl cellulose) are added in 150mL absolute ethyl alcohols, 2000r/min high-speed stirreds
2h, obtains solution B；
(3) 10.24g Delaniums are added in 150mL absolute ethyl alcohols, 2000r/min high-speed stirred 2h obtain suspended
Liquid C；
(4) solution B made from suspension A made from step (1) and step (2) is added to suspended made from step (3)
In liquid C, 1000r/min high-speed stirred 1h obtain mixed liquor D；Then mixed liquor D is dried in drying box, temperature is 80 DEG C,
Drying time is 12h, and grinds powder-grinding with Portland is ground, and obtains presoma E；
(5) presoma E made from step (4) is placed in tube furnace, is passed through the nitrogen that purity is 99.99%, and with 5
DEG C/min speed reacts 10h after being warming up to 900 DEG C, obtains the lithium ion battery silicon-carbon composite negative pole using Delanium as carrier
Material.
(3) lithium anode material will be vulcanized made from step (1) and is scanned Electron microscopy, testing result is as schemed
Shown in 3.As can be seen from Figure 3, Spray dried products are in spherical particle in pattern, and particle surface is relatively smooth, and size is at 60 μm
Left and right.Silicon-carbon composite cathode material made from step (2) is scanned Electron microscopy, and testing result is as shown in Figure 4.
Fig. 4 shows that silicon nanoparticle diameter leaves space in 30~100nm by being adhered between graphite surface, and nano-silicon, can
The expansion of silicon during receiving cell reaction.
(4) prepared by battery electrode piece, comprises the following steps that：
(1) carbon coating for preparing step (1) vulcanizes lithium anode material, binding agent polyvinylidene fluoride and conductive carbon black
Super-P (conductive agent) is according to mass ratio 8:1:1 mixing, using 1-METHYLPYRROLIDONE as the solvent (mass ratio of solute and solvent
For：1:2) slurry is tuned into, (coating thickness is 100 μm) is coated on the aluminium foil of 10 μ m-thicks, and through vacuum 80 DEG C of dry 10h, roller
Press (thickness is 85m), be prepared into lithium-sulfur cell positive plate 2；
(2) silicon-carbon composite cathode material, the binding agent LA132 prepared step (2) (binding agent solids content is 15%)
With conductive carbon black Super-P according to weight ratio 8:1:1 uniform mixing, using deionized water as the solvent (mass ratio of solute and solvent
For：1:2) slurry is tuned into, is coated on copper foil, coating thickness is 100 μm, and (thickness is through 100 DEG C of dry 10h of vacuum, roll-in
85 μm), it is prepared into lithium-sulfur cell negative plate 2.
(5) assembling of the full battery of lithium-sulphur, is comprised the following steps that：
Under normal temperature condition, by CR2032 anode covers, lithium-sulfur cell positive plate 1, electrolyte, barrier film, lithium-sulfur cell negative pole
Piece 1, pad and CR2032 negative electrode casings are assembled and sealed in order, obtain the full battery of lithium sulfide/nano-silicone wire/carbon.
Embodiment 3
(1) carbon coating vulcanizes the preparation of lithium anode material, comprises the following steps that：
(1) 16.7g lithium sulfates are scattered in 200mL deionized waters, 1500r/min high-speed stirred 0.5h obtain solution
A；
(2) 120g polyvinyl alcohol (mean molecule quantity 20000) is dissolved in 200mL deionized waters, and at 60 DEG C,
1500r/min high-speed stirred 1h, obtain mixed solution B；
(3) solution A made from step (1) is added in solution B made from step (2) and be well mixed, obtain mixing molten
Liquid C, then carries out closed cycle spray by mixed liquor C and dries powder processed, obtain presoma D；Wherein, closed cycle spray dries system
The rotating speed of centrifugal atomizer is 20000r/min during powder, and out temperature is respectively 220 DEG C and 100 DEG C, and charging rate is 15mL/
min；
(4) presoma D made from step (3) is placed in tube furnace, is passed through the nitrogen that purity is 99.99%, and with 5
DEG C/min speed reacts 4h after being warming up to 750 DEG C, obtains carbon coating vulcanization lithium anode material
(2) Delanium is the preparation of the silicon-carbon composite cathode material of carrier, is comprised the following steps that：
(1) 12.8g nano-silicons (particle diameter is 30~100nm) are scattered in 150mL absolute ethyl alcohols, in cell pulverization ultrasound
Ultrasound (power 300W) 18min, obtains suspension A in machine；
(2) 38.4g citric acids are dissolved in 150mL absolute ethyl alcohols, 400r/min high-speed stirred 0.5h obtain solution B；
(3) 10.24g Delaniums are added in 150mL absolute ethyl alcohols, 400r/min high-speed stirred 0.5h are hanged
Turbid liquid C；
(4) solution B made from suspension A made from step (1) and step (2) is added to suspended made from step (3)
In liquid C, 1000r/min high-speed stirred 1h obtain mixed liquor D；Then mixed liquor D is dried in drying box, temperature is 80 DEG C,
Drying time is 12h, and grinds powder-grinding with Portland is ground, and obtains presoma E；
(5) presoma E made from step (4) is placed in tube furnace, the nitrogen that purity is 99.99% is passed through into tube furnace
Gas, and 6h is reacted after being warming up to 700 DEG C with 2 DEG C/min speed, obtain the lithium ion battery silicon-carbon using Delanium as carrier
Composite negative pole material.
(3) prepared by battery electrode piece, comprises the following steps that：
(1) carbon coating for preparing step (1) vulcanizes lithium anode material, binding agent polyvinylidene fluoride and conductive carbon black
Super-P (conductive agent) is according to mass ratio 8:1:1 mixing, using 1-METHYLPYRROLIDONE as the solvent (mass ratio of solute and solvent
For：1:2) slurry is tuned into, (coating thickness is 100 μm) is coated on the aluminium foil of 10 μ m-thicks, and through vacuum 80 DEG C of dry 10h, roller
Pressure (thickness is 85 μm), is prepared into lithium-sulfur cell positive plate 3；
(2) silicon-carbon composite cathode material, the binding agent LA132 prepared step (2) (binding agent solids content is 15%)
With conductive carbon black Super-P according to weight ratio 8:1:1 uniform mixing, using deionized water as the solvent (mass ratio of solute and solvent
For：1:2) be tuned into slurry, be coated on copper foil, coating thickness is 100 μm, and through vacuum 100 DEG C of dry 10h, roll-in (thickness
For 85 μm), it is prepared into lithium-sulfur cell negative plate 3.
(3) full battery assembling and battery performance test, are comprised the following steps that：
Under normal temperature condition, using the positive and negative pole material in LAND battery test systems testing procedure (three).By CR2032 just
Pole shell, into lithium-sulfur cell positive plate 3, electrolyte, barrier film, lithium-sulfur cell negative plate 3, pad and CR2032 negative electrode casings in order
Assemble and seal, electrochemical property test is carried out after precipitation 12h.Voltage belt of the cyclic voltammetry of battery in 1.0~4.0V
Between carry out, as a result as shown in Figure 5.The oxidation peak of battery is located at 3.5~3.8V, and reduction peak is located at 1.5~1.7V.Constant current charge-discharge
Test is carried out under 100mA/g current densities, and charging/discharging voltage interval is 0.6~4.8V, test result as shown in fig. 6, test
Initial charge specific capacity is obtained for 897mAh/g, discharge platform is located at 1.6~2.2V, charging platform is located at 2.8~4.0V, displaying
Go out good volumetric properties.
Above-described embodiment is preferably embodiment, but embodiments of the present invention are not by above-described embodiment of the invention
Limitation, other any Spirit Essences without departing from the present invention and the change made under principle, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the full battery of lithium sulfide/nano-silicone wire/carbon, it is characterised in that comprise the following steps：
(1) lithium sulfate is distributed in water, obtains solution A, organic carbon source is distributed in polar organic solvent, obtain solution B,
Solution A and solution B are well mixed again, mixed solution C is obtained；
(2) powder processed is dried in the mixed solution C obtained in step (1), obtains presoma D；
(3) the presoma D obtained in step (2) is calcined, obtains carbon coating lithium sulfide composite positive pole E；
(4) nano-silicon is distributed in organic solvent, obtains suspension F, organic carbon source is distributed in organic solvent, obtain molten
Liquid G, Delanium is distributed in organic solvent, obtains suspension H, then suspension F, solution G and suspension H are mixed into equal
It is even, obtain mixed liquor I；
(5) powder processed is dried in the mixed liquor I obtained in step (4), obtains presoma J；
(6) the presoma J obtained in step (5) is calcined, obtains carbon coating silicon-carbon composite cathode material K；
(7) adjusted after being well mixed the carbon coating lithium sulfide composite positive pole E, binding agent and the conductive agent that are obtained in step (3)
Into slurry, it is coated with aluminium foil, dries, roll-in obtains lithium-sulfur cell positive plate；
(8) it is tuned into after being well mixed the carbon coating silicon-carbon composite cathode material K, binding agent and the conductive agent that are obtained in step (6)
Slurry, is coated with aluminium foil, dries, and roll-in obtains lithium-sulfur cell negative plate；
(9) lithium-sulfur cell that will be obtained in the lithium-sulfur cell positive plate obtained in step (7), barrier film, electrolyte and step (8)
Negative plate is packaged, and obtains the full battery of lithium sulfide/nano-silicone wire/carbon.
2. the preparation method of the full battery of lithium sulfide/nano-silicone wire/carbon according to claim 1, it is characterised in that：
Organic carbon source described in step (1) is at least one of sucrose, glucose, pitch and polyvinyl alcohol；
Polar organic solvent described in step (1) is water or tetrahydrofuran；
Organic carbon source described in step (4) is at least one of citric acid, carboxymethyl cellulose, pitch and glucose；
Organic solvent described in step (4) is one kind in absolute ethyl alcohol, acetone and tetrahydrofuran.
3. the preparation method of the full battery of lithium sulfide/nano-silicone wire/carbon according to claim 1, it is characterised in that：
The mass ratio of lithium sulfate and organic carbon source described in step (1) is 1：7.0~7.5；
The mass ratio of nano-silicon, organic carbon source and Delanium described in step (4) is 1：2~4：0.5~0.8.
4. the preparation method of the full battery of lithium sulfide/nano-silicone wire/carbon according to claim 1, it is characterised in that：
The mass ratio of carbon coating lithium sulfide composite positive pole E, binding agent and conductive agent described in step (7) are 70~84：
15~8：15~8；
Carbon coating silicon-carbon composite cathode material K, binding agent described in step (8) and the mass ratio of conductive agent mixing for 76~
84：12~8：12~8.
5. the preparation method of the full battery of lithium sulfide/nano-silicone wire/carbon according to claim 1, it is characterised in that：
Calcining described in step (3) and step (6) is to be calcined under inert gas shielding；
The condition of calcining described in step (3) is：600~850 DEG C are warming up to 2~10 DEG C/min speed, then constant temperature is protected
Hold 1~5h；
The condition of calcining described in step (6) is：700~900 DEG C are warming up to 2~5 DEG C/min speed, then constant temperature is kept
3~10h.
6. the preparation method of the full battery of lithium sulfide/nano-silicone wire/carbon according to claim 1, it is characterised in that：
Drying described in step (2) is to be dried using closed cycle spray drying machine；The closed cycle spray is dried
Machine is centrifugal atomizer, and its rotating speed is 15000~40000r/min, and out temperature is respectively 100~300 DEG C and 60~120
DEG C, charging rate is 10~20mL/min；
The condition of drying described in step (5) is：6~14h is dried in 60~90 DEG C of drying box；
The condition of drying described in step (7) and step (8) is：5~24h is dried under 50~100 DEG C of vacuum condition.
7. the preparation method of the full battery of lithium sulfide/nano-silicone wire/carbon according to claim 1, it is characterised in that：
The particle size of nano-silicon described in step (4) is 30~100nm；
The dispersing mode of nano-silicon described in step (4) is ultrasonic disperse；
Binding agent described in step (7) is polyvinylidene fluoride or PVP K30；
Conductive agent described in step (7) is conductive carbon black Super-P, Ketjen black or acetylene black.
8. the preparation method of the full battery of lithium sulfide/nano-silicone wire/carbon according to claim 1, it is characterised in that：
The thickness of coating described in step (7) is 120~200 microns；
The thickness of roll-in described in step (7) is 90~140 microns；
The thickness of coating described in step (8) is 100~180 microns；
The thickness of roll-in described in step (8) is 75~150 microns.
9. a kind of full battery of lithium sulfide/nano-silicone wire/carbon, it is characterised in that：Pass through the method system described in any one of claim 1~8
It is standby to obtain.
10. the answering in electric automobile or portable type electronic product of the full battery of lithium sulfide/nano-silicone wire/carbon described in claim 9
With.
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