CN109216685A - Rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method - Google Patents

Rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method Download PDF

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CN109216685A
CN109216685A CN201811154258.1A CN201811154258A CN109216685A CN 109216685 A CN109216685 A CN 109216685A CN 201811154258 A CN201811154258 A CN 201811154258A CN 109216685 A CN109216685 A CN 109216685A
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lithium ion
silicon
ion battery
carbon negative
negative electrode
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尹华意
赵竹青
谢宏伟
宁志强
宋秋实
邢鹏飞
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Northeastern University China
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Northeastern University China
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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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

一种稻谷壳制备锂离子电池硅‑碳负极材料的熔盐电化学方法，属于锂离子电池的领域。该制备方法将稻谷壳清洗烘干后作为原料，对其进行碳化，将碳化谷壳灰球磨成粉末，压片，烧结，以压片作为阴极，石墨棒作为阳极，在氯化钙熔盐中，高温下施加电压，恒电位电解，使稻谷壳中的二氧化硅还原为硅，还原得到的硅被谷壳中的碳包覆形成碳包覆硅的核壳结构，将压片提离熔盐冷却、清洗除去盐、盐酸酸洗、干燥，实现锂离子电池硅‑碳负极材料的制备。该方法可以制成性能优良的锂离子电池硅‑碳负极材料，环境友好、成本较低、操作简单。A molten salt electrochemical method for preparing silicon-carbon negative electrode materials of lithium ion batteries from rice husks belongs to the field of lithium ion batteries. In the preparation method, the rice husk is washed and dried as a raw material, then carbonized, the carbonized rice husk ash balls are ground into powder, pressed into tablets, and sintered, the tablet is used as a cathode, a graphite rod is used as an anode, and in calcium chloride molten salt , applying a voltage at a high temperature and electrolyzing at a constant potential to reduce the silicon dioxide in the rice husk to silicon, and the reduced silicon is covered by the carbon in the rice husk to form a carbon-coated silicon core-shell structure, and the tablet is lifted off the melting point. Salt cooling, cleaning to remove salt, hydrochloric acid pickling, and drying to realize the preparation of lithium-ion battery silicon-carbon negative electrode material. The method can make silicon-carbon negative electrode material of lithium ion battery with excellent performance, which is environmentally friendly, low in cost and simple in operation.

Description

Rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method
Technical field
The present invention relates to the fields of lithium ion battery, and in particular to a kind of rice hulls prepare lithium ion battery silicon-Carbon anode The melten salt electriochemistry method of material.
Background technique
The advantages that lithium ion battery is highly-safe due to big with specific energy, long service life, environmental pollution is small, It is widely used in the numerous areas such as various portable electronic devices and new-energy automobile.The progress of lithium ion battery is very big The performance of electrode material is depended in degree.Currently, commercialized lithium ion battery mainly uses graphite as negative electrode material.So And lower theoretical capacity (372mAh/g) is difficult to meet the strict demand of next-generation lithium ion battery.Therefore, searching has The lithium ion battery negative material of new generation of high capacity, high power density and excellent rate capacity seems extremely urgent.
In various negative electrode materials of new generation, silicon materials are due to high theoretical capacity (4200mAh/g) and rich Rich resource, it is considered to be the next-generation lithium ion battery negative material of great future.However, due to the embedding de- lithium in charge and discharge In the process, silicon materials volume expansion is shunk big, be will cause the fracture and dusting of silicon materials itself, is led to its poor circulation, library The problems such as human relations low efficiency.Furthermore silicon itself does not have good electric conductivity.In view of the above problems, specifically how buffer cycles mistake The volume expansion of silicon materials in journey enhances its electric conductivity, becomes the hot spot studied in the industry.
Summary of the invention
The object of the present invention is to provide a kind of rice hulls to prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry side Method, the preparation method are carbonized to it using cheap rice hulls as raw material, after the rice hull ash ball that carbonization obtains is clayed into power Tabletting, using tabletting as cathode, graphite rod is as anode, in calcium chloride fused salt, applies voltage, potentiostatic deposition one under high temperature The section time, make the reducing silica silicon in rice hulls, the silicon restored forms carbon coating silicon by the carbon coating in husk Core-shell structure, tabletting lift-off fused salt is cooling, cleaning except desalt, chlorohydric acid pickling, drying, realize that lithium ion battery silicon-carbon is negative The preparation of pole material.Lithium ion battery silicon-carbon negative pole material of function admirable, environment friend can be made using method of the invention Well, cost is relatively low, easy to operate.
A kind of rice hulls of the invention prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, including with Lower step:
Step 1: the carbonization of rice hulls
(1) by after rice hulls cleaning, drying, cooling, dry rice hulls are obtained；
(2) dry rice hulls are fitted into crucible, are placed in Muffle furnace by crucible, is carbonized in 300~400 DEG C of constant temperature 10~15h obtains carbonized rice husks ash；
Step 2: the preparation of carbonized rice husks ash tabletting
Carbonized rice husks ash is placed in ball mill, ball milling, obtains rice husk ash powder；Wherein, the partial size of rice husk ash powder is 10nm~1000nm；
Rice husk ash powder is subjected to tabletting, sintering obtains rice husk ash pressed powder；
Step 3: preparing before electrolysis
(1) rice husk ash pressed powder is fixed on metal molybdenum rod collector with thin molybdenum filament, cathode is made；
Graphite rod is connect with metal molybdenum rod collector, anode is made；
(2) moisture removal is removed into calcium chloride salt drying, is placed in crucible, then crucible is placed in reactor；
(3) cathode and anode are suspended on above calcium chloride, and are not contacted with calcium chloride, closed reactor, will reacted After device vacuumizes, 200~400 DEG C, 60~120min of constant temperature are warming up to, vacuum pump is closed, is continually fed into argon gas to reactor, makes It obtains and forms argon atmosphere in reactor；
Step 4: electrolysis
Reactor is heated to the fusion temperature of calcium chloride, forms fused salt, by cathode, anode insertion fused salt, forms two Electrode system, wherein setting two electrodes between horizontal interval be 30 ± 0.1mm, between cathode and anode apply voltage 2.4~ 2.7V, permanent slot piezoelectricity 10~15h of solution, the cathode after electrolysis take out cooling from fused salt；
Step 5: product processing
The cathode after electrolysis is put into deionized water, cleaning removes fused salt, cleans with dilute hydrochloric acid, removes cathode and produces Undesired oxide in object, vacuum drying, obtains lithium ion battery silicon-carbon negative pole material, encapsulates.
In (1) of the step 1, the drying, drying temperature be 100 DEG C~120 DEG C, drying time be 5~ 10h。
In (1) of the step 1, the crucible is preferably ceramic crucible.
In the step 2, the ball milling, ball-milling technology be 100r/min~150r/min, Ball-milling Time be 2h~ 5h。
In the step 2, the tabletting, pressure is 3~5MPa, and the dwell time is 1~2min.
In the step 2, the sintering, sintering temperature is 900~1000 DEG C, and sintering time is 10~15h.
In (1) of the step 3, the diameter of the thin molybdenum filament is 0.3 ± 0.01mm, the metal molybdenum rod afflux The diameter of body is 1.5 ± 0.1mm；The graphite rod is high purity graphite rod, and a diameter of 10 ± 0.1mm, purity is spectroscopic pure.
In (2) of the step 3, the crucible is metal oxide crucible, preferably alumina crucible.
In (2) of the step 3, purity >=99wt.% of the calcium chloride.
In (2) of the step 3, described by calcium chloride drying, to remove moisture removal be that calcium chloride is placed in high-temperature vacuum to do In dry furnace, in 300~400 DEG C of temperature and pressure -0.1MPa hereinafter, dry 10~15h, removes absorption water and partially crystallizable water.
In (3) of the step 3, in vacuum, the purpose of heating is the ionized water and freedom of reactor Water is cleaned.
In (3) of the step 3, the argon gas is passed through by reactor air inlet, is discharged by reactor gas outlet, row When out, the moisture that calcium chloride generates is taken away.
In the step 4, the fusion temperature is 850 ± 5 DEG C.
In the step 4, the reactor heating, is that reactor is placed in resistance wire furnace to heat.
In the step 5, the molar concentration of the dilute hydrochloric acid is 0.1~0.2mol/L.
Rice hulls of the present invention prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, Ke Yijin Row continuous electrolysis after continuous electrolysis takes out for cathode after electrolysis, continues to be electrolysed in cathode insertion fused salt that will be other.
A kind of lithium ion battery silicon-carbon negative pole material of the invention is made according to above-mentioned preparation method.
A kind of lithium ion battery of the invention, including anode, cathode, diaphragm and electrolyte, wherein the cathode uses Above-mentioned lithium ion battery silicon-carbon negative pole material.
A kind of rice hulls of the invention prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, principle Be: by the carbon given birth to using organic carbon in the silica and rice hulls contained in rice hulls, ball is clayed into power, pressure Cathode is used as after piece, the method for taking melten salt electriochemistry restores the silica in husk and generates silicon nanoparticle.SiO2Reduction When volume reduce, carbon coating generated and silicon face form hollow core-shell structure after the complete organic carbon of unreacted. This structure will greatly buffer silicium cathode volume change violent during removal lithium embedded；In addition, the carbon of silicon particle outer layer Cladding is beneficial to improve its electric conductivity.
A kind of rice hulls of the invention prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, beneficial Effect is:
High yield agricultural wastes rice hulls can be recycled using method of the invention, by utilizing rice hulls In silica and organic matter pyrolysis after carbon, pass through the method for melten salt electriochemistry, restore silica, formed carbon coating Silicon core-shell structure buffers the volume change of silicon materials itself in charge and discharge process, while leading using outer cladding carbon reinforcing material Electrically, to prepare lithium ion battery silicon-carbon negative pole material of function admirable, and environmentally friendly, low in cost, operation Simply, can turn waste into wealth.
Detailed description of the invention
Fig. 1 is lithium ion battery silicon-carbon negative pole material structural schematic diagram of rice hulls of the present invention preparation.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail.
In present example, unless specifically indicated, the raw material and equipment of use be it is commercially available, purity be analyze it is pure and with On；The rice hulls specially used is commercial products.The thin molybdenum filament that uses, metal molybdenum rod collector is commercial products.It uses Ceramic crucible, alumina crucible are commercial products.The graphite rod used is commercial products.The salt used is calcium chloride, purity It is pure to analyze.
Graphite rod 10 ± the 0.1mm of diameter used in the embodiment of the present invention, purity is spectroscopic pure.
The diameter of the thin molybdenum filament used in the embodiment of the present invention is in 0.3 ± 0.01mm, purity 99.99%.
The diameter of the metal molybdenum rod collector used in the embodiment of the present invention is in 1.5 ± 0.1mm, purity 99.99%.
Use calcium chloride for fused salt in the embodiment of the present invention, operation temperature is controlled at 850 ± 5 DEG C.
The voltage applied between two electrodes used in the embodiment of the present invention is 2.4 ± 0.1V~2.7 ± 0.1V.
The power supply used in the embodiment of the present invention is new prestige Power Battery Testing System, model are as follows: BTS 4000.
In the embodiment of the present invention, the gas outlet of reactor is extended in the pond outside reactor under liquid level by pipeline Side, when argon gas persistently circulates, has bubble to emerge.
In the embodiment of the present invention, it is that calcium chloride is placed in high-temperature vacuum drying oven that moisture removal is removed in calcium chloride drying, 12h is dried under the conditions of 300 DEG C of temperature and pressure -0.1MPa, removes absorption water and partially crystallizable water.
Carrying out heating to the material in reactor in the embodiment of the present invention is that reactor is placed in resistance wire furnace to heat.
Embodiment 1
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, sequentially include the following steps:
Step 1: the carbonization of rice hulls
(1) rice hulls for weighing 50g after being washed with deionized water, then will in drying box with 100 DEG C of freeze-day with constant temperature 6h It takes out to be placed in air and be cooled to room temperature, and obtains dry rice hulls；
(2) muffle furnace is warming up to 300 DEG C, dry rice hulls is then packed into ceramic crucible, being placed in temperature is In 300 DEG C of Muffle furnace, the constant temperature carbonization 12h at 300 DEG C obtains carbonized rice husks ash；
Step 2: the preparation of rice hulls ash pressed powder
Carbonized rice husks ash is placed in ball mill, the ball milling 4h at 100r/min, obtains the husk ashes that partial size is 500nm End.After to ball milling, the rice husk ash powder of 0.8 ± 0.1g is weighed, carries out tabletting at 3MPa, dwell time 2min, then The piece pressed is sintered 12h at 1000 DEG C, obtains rice husk ash pressed powder；
Step 3: preparing before electrolysis
(1) rice husk ash pressed powder is tied up on 1.5 ± 0.1mm metal molybdenum rod collector with the thin molybdenum filament of 0.3 ± 0.01mm, Cathode is made；
10 ± 0.1mm of diameter graphite rod is connect with 1.5 ± 0.1mm metal molybdenum rod collector, anode is made；
(2) 500g is analyzed into the drying in 300 DEG C, the vacuum drying oven of -0.1MPa of pure calcium chloride salt and removes moisture removal, be placed in In the alumina crucible of 100 ± 0.1mm of diameter, then alumina crucible is placed in reactor；
(3) cathode, anode are not connect first by being suspended on above calcium chloride in flange intercalation reaction device with calcium chloride salt Touching, closed reactor after vacuumizing reactor, are warming up to 300 DEG C, and constant temperature 60min, close vacuum pump, hold to reactor It is continuous to be passed through argon gas, so that forming argon atmosphere in reactor；
Step 4: electrolysis
Reactor is heated to 850 ± 5 DEG C, calcium chloride melts to form fused salt, by cathode, anode insertion fused salt, is formed Two electrode systems, horizontal interval is 30 ± 0.1mm between two electrodes, applies voltage 2.4V, permanent slot piezoelectricity solution between cathode and anode 12h, the cathode after electrolysis take out cooling from fused salt, while by other cathode insertion fused salt, continuing to be electrolysed；
Step 5: product processing
It is put into deionized water after the cathode product that electrolysis obtains is cooled down, cleaning removes fused salt, then with 0.1mol/L's Dilute hydrochloric acid cleaning removes oxide extra in cathode product, and vacuum drying obtains lithium ion battery silicon-carbon negative pole material, seals Dress.Lithium ion battery silicon-carbon negative pole material structural schematic diagram of preparation is shown in Fig. 1, forms the core-shell structure of carbon coating silicon.
Application examples
Lithium ion battery silicon-carbon negative pole material prepared by embodiment 1 is pressed with conductive agent acetylene black and binder PVDF Mass ratio, lithium ion battery silicon-carbon negative pole material: conductive agent acetylene black: binder PVDF=7:2:1 ratio is uniformly mixed It closes, solvent N-methyl pyrilidone is added and is prepared into slurry, slurry is applied in copper foil current collector, obtains electrode slice；
Electrode slice is placed in vacuum drying, electrode slice is washed into after electrode slice is completely dried with 90 DEG C of dry 12h Diameter is the electrode wafer piece of 12mm.
Using obtained electrode wafer piece as cathode, metal lithium sheet is as anode, and Celgard2400 is as diaphragm, EC/ DMC(1:1)-LiPF6(1M) is electrolyte, and battery assembly is carried out in glove box.
Using blue CT2001A type battery test system to carry out constant current charge-discharge survey in 0.01~1.5V voltage range Examination.Electrochemical results show with 0.1Ag-1After 500 circulations, the Reversible Cycle capacity of battery is current density 1216.1mAh·g-1, coulombic efficiency is maintained at 99%.
Embodiment 2
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, different with embodiment 1 Point is:
(1) in step 4 electrolytic process, the voltage of application is 2.5 ± 0.1V；
Other modes are identical.
Embodiment 3
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, different with embodiment 1 Point is:
(1) in step 4 electrolytic process, the voltage of application is 2.6 ± 0.1V；
Other modes are identical.
Embodiment 4
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, different with embodiment 1 Point is:
(1) in step 4 electrolytic process, the voltage of application is 2.7 ± 0.1V；
Other modes are identical.
Embodiment 5
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, different with embodiment 1 Point is:
(1) carburizing temperature in step 1 is 325 DEG C；
(2) in step 4 electrolytic process, the voltage of application is 2.4 ± 0.1V；
Other modes are identical.
Embodiment 6
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, different with embodiment 1 Point is:
(1) the rice hulls carburizing temperature in step 1 is 325 DEG C；
(2) in step 4 electrolytic process, the voltage of application is 2.5 ± 0.1V；
Other modes are identical.
Embodiment 7
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, different with embodiment 1 Point is:
(1) the rice hulls carburizing temperature in step 1 is 325 DEG C；
(2) in step 4 electrolytic process, the voltage of application is 2.6 ± 0.1V；
Other modes are identical.
Embodiment 8
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, different with embodiment 1 Point is:
(1) the rice hulls carburizing temperature in step 1 is 325 DEG C；
(2) in step 4 electrolytic process, the voltage of application is 2.7 ± 0.1V；
Other modes are identical.
Embodiment 9
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, different with embodiment 1 Point is:
(1) the rice hulls carburizing temperature in step 1 is 350 DEG C；
(2) in step 4 electrolytic process, the voltage of application is 2.4 ± 0.1V；
Other modes are identical.
Embodiment 10
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, different with embodiment 1 Point is:
(1) the rice hulls carburizing temperature in step 1 is 350 DEG C；
(2) in step 4 electrolytic process, the voltage of application is 2.5 ± 0.1V；
Other modes are identical.
Embodiment 11
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, different with embodiment 1 Point is:
(1) the rice hulls carburizing temperature in step 1 is 350 DEG C；
(2) in step 4 electrolytic process, the voltage of application is 2.6 ± 0.1V；
Other modes are identical.
Embodiment 12
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, different with embodiment 1 Point is:
(1) the rice hulls carburizing temperature in step 1 is 350 DEG C；
(2) in step 4 electrolytic process, the voltage of application is 2.7 ± 0.1V；
Other modes are identical.
Embodiment 13
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, different with embodiment 1 Point is:
(1) the rice hulls carburizing temperature in step 1 is 375 DEG C；
(2) in step 4 electrolytic process, the voltage of application is 2.4 ± 0.1V；
Other modes are identical.
Embodiment 14
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, different with embodiment 1 Point is:
(1) the rice hulls carburizing temperature in step 1 is 375 DEG C；
(2) in step 4 electrolytic process, the voltage of application is 2.5 ± 0.1V；
Other modes are identical.
Embodiment 15
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, different with embodiment 1 Point is:
(1) the rice hulls carburizing temperature in step 1 is 375 DEG C；
(2) in step 4 electrolytic process, the voltage of application is 2.6 ± 0.1V；
Other modes are identical.
Embodiment 16
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, different with embodiment 1 Point is:
(1) the rice hulls carburizing temperature in step 1 is 375 DEG C；
(2) in step 4 electrolytic process, the voltage of application is 2.7 ± 0.1V；
Other modes are identical.
Embodiment 17
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, different with embodiment 1 Point is:
(1) the rice hulls carburizing temperature in step 1 is 400 DEG C；
(2) in step 4 electrolytic process, the voltage of application is 2.4 ± 0.1V；
Other modes are identical.
Embodiment 18
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, different with embodiment 1 Point is:
(1) the rice hulls carburizing temperature in step 1 is 400 DEG C；
(2) in step 4 electrolytic process, the voltage of application is 2.5 ± 0.1V；
Other modes are identical.
Embodiment 19
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, different with embodiment 1 Point is:
(1) the rice hulls carburizing temperature in step 1 is 400 DEG C；
(2) in step 4 electrolytic process, the voltage of application is 2.6 ± 0.1V；
Other modes are identical.
Embodiment 20
A kind of rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method, different with embodiment 1 Point is:
(1) the rice hulls carburizing temperature in step 1 is 400 DEG C；
(2) in step 4 electrolytic process, the voltage of application is 2.7 ± 0.1V；
Other modes are identical.

Claims (10)

1.一种稻谷壳制备锂离子电池硅-碳负极材料的熔盐电化学方法，其特征在于，包括以下步骤：1. a kind of rice husk prepares the molten salt electrochemical method of lithium ion battery silicon-carbon negative electrode material, is characterized in that, comprises the following steps: 步骤1：稻谷壳的碳化Step 1: Carbonization of Rice Husks (1)将稻谷壳清洗、烘干、冷却后，得到干燥的稻谷壳；(1) after the rice husks are cleaned, dried and cooled, dry rice husks are obtained; (2)将干燥的稻谷壳装入坩埚中，在将坩埚置于马弗炉中，在300～400℃恒温碳化10～15h，得到碳化谷壳灰；(2) putting the dried rice husks into a crucible, placing the crucible in a muffle furnace, and carbonizing at a constant temperature of 300-400° C. for 10-15 hours to obtain carbonized rice husk ash; 步骤2：碳化谷壳灰压片的制备Step 2: Preparation of Carbonized Rice Husk Ash Tablets 将碳化谷壳灰置于球磨机中，球磨，得到谷壳灰粉末；其中，谷壳灰粉末的粒径为10nm～1000nm；The carbonized rice husk ash is placed in a ball mill, and ball-milled to obtain rice husk ash powder; wherein, the grain size of the rice husk ash powder is 10 nm to 1000 nm; 将谷壳灰粉末进行压片，烧结，得到谷壳灰粉末压片；The chaff ash powder is tableted and sintered to obtain chaff ash powder tableting; 步骤3：电解前准备Step 3: Preparation before electrolysis (1)将谷壳灰粉末压片用细钼丝固定在金属钼杆集流体上，制得阴极；(1) the chaff ash powder tableting is fixed on the metal molybdenum rod current collector with thin molybdenum wire to obtain the cathode; 将石墨棒与金属钼杆集流体连接，制得阳极；Connect the graphite rod to the metal molybdenum rod current collector to obtain an anode; (2)将氯化钙盐烘干去除水分，置于坩埚中，再将坩埚置于反应器中；(2) the calcium chloride salt is dried to remove moisture, placed in the crucible, and then the crucible is placed in the reactor; (3)将阴极和阳极悬挂在氯化钙上方，并且不与氯化钙接触，封闭反应器，将反应器抽真空后，升温至200～400℃，恒温60～120min，关闭真空泵，向反应器持续通入氩气，使得反应器内形成氩气气氛；(3) hang the cathode and the anode above the calcium chloride without contacting the calcium chloride, close the reactor, after the reactor is evacuated, be heated to 200～400 ℃, constant temperature 60～120min, close the vacuum pump, and react to the The reactor is continuously fed with argon, so that an argon atmosphere is formed in the reactor; 步骤4：电解Step 4: Electrolysis 将反应器加热至氯化钙的熔化温度，形成熔盐，将阴极、阳极***熔盐中，形成两电极体系，其中，设置两电极间水平间隔为30±0.1mm，在阴极和阳极间施加电压2.4～2.7V，恒槽压电解10～15h，电解后的阴极从熔盐中取出冷却；The reactor is heated to the melting temperature of calcium chloride to form molten salt, and the cathode and anode are inserted into the molten salt to form a two-electrode system, wherein the horizontal interval between the two electrodes is set to be 30 ± 0.1mm, and the application between the cathode and the anode is applied. The voltage is 2.4-2.7V, the constant cell voltage is electrolyzed for 10-15h, and the electrolyzed cathode is taken out from the molten salt for cooling; 步骤5：产物处理Step 5: Product Processing 将电解后的阴极，放入去离子水中，清洗除去熔盐，在用稀盐酸清洗，除去阴极产物中多余氧化物，真空干燥，得到锂离子电池硅-碳负极材料，封装。The electrolyzed cathode is put into deionized water, washed to remove molten salt, washed with dilute hydrochloric acid to remove excess oxide in the cathode product, and vacuum-dried to obtain a silicon-carbon anode material for lithium ion battery, which is packaged. 2.如权利要求1所述的稻谷壳制备锂离子电池硅-碳负极材料的熔盐电化学方法，其特征在于，所述的步骤1的(1)中，所述的干燥，干燥温度为100℃～120℃，干燥时间为5～10h。2. the fused salt electrochemical method of preparing lithium ion battery silicon-carbon negative electrode material from rice husk as claimed in claim 1, is characterized in that, in described step 1 (1), described drying, drying temperature is 100℃～120℃, drying time is 5～10h. 3.如权利要求1所述的稻谷壳制备锂离子电池硅-碳负极材料的熔盐电化学方法，其特征在于，所述的步骤2中，所述的球磨，球磨工艺为100r/min～150r/min，球磨时间为2h～5h。3. The molten salt electrochemical method for preparing lithium-ion battery silicon-carbon negative electrode material from rice husks as claimed in claim 1, characterized in that, in the described step 2, in the described ball milling, the ball milling process is 100 r/min～ 150r/min, ball milling time is 2h ~ 5h. 4.如权利要求1所述的稻谷壳制备锂离子电池硅-碳负极材料的熔盐电化学方法，其特征在于，所述的步骤2中，所述的压片，压力为3～5MPa，保压时间为1～2min。4. The molten salt electrochemical method for preparing silicon-carbon negative electrode material of lithium ion battery from rice husks as claimed in claim 1, characterized in that, in the described step 2, the pressure of the tablet pressing is 3～5MPa, The holding time is 1 to 2 minutes. 5.如权利要求1所述的稻谷壳制备锂离子电池硅-碳负极材料的熔盐电化学方法，其特征在于，所述的步骤2中，所述的烧结，烧结温度为900～1000℃，烧结时间为10～15h。5 . The molten salt electrochemical method for preparing silicon-carbon negative electrode material for lithium ion batteries from rice husks as claimed in claim 1 , wherein in the step 2, the sintering temperature is 900-1000° C. 5 . , the sintering time is 10 ~ 15h. 6.如权利要求1所述的稻谷壳制备锂离子电池硅-碳负极材料的熔盐电化学方法，其特征在于，所述的步骤3的(1)中，所述的细钼丝的直径为0.3±0.01mm，所述的金属钼杆集流体的直径为1.5±0.1mm；所述的石墨棒为高纯石墨棒，其直径为10±0.1mm，纯度为光谱纯。6. The molten salt electrochemical method for preparing lithium ion battery silicon-carbon negative electrode material from rice husk as claimed in claim 1, is characterized in that, in (1) of described step 3, the diameter of described thin molybdenum wire The diameter of the metal molybdenum rod current collector is 1.5±0.1mm; the graphite rod is a high-purity graphite rod, its diameter is 10±0.1mm, and the purity is spectrally pure. 7.如权利要求1所述的稻谷壳制备锂离子电池硅-碳负极材料的熔盐电化学方法，其特征在于，所述的步骤3的(2)中，所述的将氯化钙烘干去除水分是将氯化钙置于高温真空干燥炉中，在温度300～400℃和压力-0.1MPa以下，干燥10～15h，除去吸附水和部分结晶水。7. the molten salt electrochemical method of preparing lithium ion battery silicon-carbon negative electrode material from rice husk as claimed in claim 1, is characterized in that, in described step 3 (2), described calcium chloride is baked Dry removal of water is to place calcium chloride in a high temperature vacuum drying furnace, and dry it for 10 to 15 hours at a temperature of 300 to 400 °C and a pressure below -0.1 MPa to remove adsorbed water and part of crystal water. 8.如权利要求1所述的稻谷壳制备锂离子电池硅-碳负极材料的熔盐电化学方法，其特征在于，所述的步骤4中，所述的熔化温度为850±5℃。8 . The molten salt electrochemical method for preparing silicon-carbon negative electrode material for lithium ion batteries from rice husks according to claim 1 , wherein in the step 4, the melting temperature is 850±5° C. 9 . 9.一种锂离子电池硅-碳负极材料，其特征在于，该锂离子电池硅-碳负极材料按照权利要求1-8任意一项所述的制备方法制得。9 . A silicon-carbon negative electrode material for lithium ion batteries, characterized in that, the silicon-carbon negative electrode material for lithium ion batteries is prepared according to the preparation method described in any one of claims 1-8. 10.一种锂离子电池，包括正极、负极、隔膜和电解液，其特征在于，所述的负极采用上述的锂离子电池硅-碳负极材料。10. A lithium ion battery, comprising a positive electrode, a negative electrode, a separator and an electrolyte, wherein the negative electrode adopts the above-mentioned lithium ion battery silicon-carbon negative electrode material.
CN201811154258.1A 2018-09-30 2018-09-30 Rice hulls prepare lithium ion battery silicon-carbon negative pole material melten salt electriochemistry method Pending CN109216685A (en)

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