CN104009225B - A kind of method of synthetic silicic acid iron lithium/crystalline carbon composite positive pole - Google Patents
A kind of method of synthetic silicic acid iron lithium/crystalline carbon composite positive pole Download PDFInfo
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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
- H01M4/364—Composites as mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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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
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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
Abstract
The present invention relates to a kind of method of synthetic silicic acid iron lithium/crystalline carbon composite positive pole, belong to technical field of lithium ion.First the rice husk removing alkali metal oxide impurity will be obtained after rice husk pickling, washing, filtration and drying; The rice husk removing alkali metal oxide impurity is carried out low temperature pyrogenation under anaerobic or aerobic conditions and obtains pyrolysis rice husk; The pyrolysis rice husk obtained is joined in the precursor salt solution of transition metal M 1, then obtains catalyzing and carbonizing product in high-temperature catalytic carbonization reaction; Catalyzing and carbonizing product low-temperature oxidation is obtained oxidation product; Source of iron and lithium source is added and wet-milling obtains mixed material in oxidation product, then that mixed material is dry; Under an inert atmosphere, be that 500 ~ 800 DEG C of roasting 1 ~ 20h can prepare silicate/crystalline carbon composite positive pole by dried mixed material in temperature.This method improves the crystallinity of carbon in silicate/carbon composite anode material prepared by above-mentioned rice husk.
Description
Technical field
The present invention relates to a kind of method of synthetic silicic acid iron lithium/crystalline carbon composite positive pole, belong to technical field of lithium ion.
Background technology
Along with the fast development of electronics and information industry, mobile communication, digital vedio recording and portable computer are used widely, the Study and Development of electric automobile also carrying out extensively and profoundly, thus drives as the said equipment provides developing rapidly of the device-lithium ion battery of the energy.Compare with nickel-cadmium cell with traditional Ni-MH battery, it is high that lithium ion battery has energy density, and operating voltage is high, self discharge is little, can the advantages such as fast charging and discharging, security performance be good, is with fastest developing speed, a kind of secondary cell that market prospects are the brightest at present.
In lithium ion battery, battery material plays decisive influence effect to the performance that battery is determined.1996, Goodenough seminar proposed olivine-type LiFePO_4 positive electrode first, and Armand proposes the another kind of orthosilicate positive electrode being polyanion group with SiO4 tetrahedron at patent US6085015, i.e. LiMSiO4(M=Fe, Mn etc.).This type of positive electrode has stable SiO
4tetrahedral framework, abundant natural resources, advantages of environment protection, in addition, it can allow 2 reversible deintercalations of Li+ in theory, and theoretical capacity reaches 330mAh/g.But it is after first time discharge and recharge, great changes will take place for structure, thus have impact on the reversible deintercalation of lithium ion, hinders its application.In fact, be that the silicate anodal material of representative can only deintercalation 1 lithium ion in use with ferric metasilicate lithium, cause its theoretical capacity only to have 166mAh/g.At present, people improve its chemical property by methods such as Surface coating, metal-doped and synthesizing nano-particles, and wherein carbon is coated is comparatively common method of modifying.
Rice husk contains amorphous nano silicon and macromolecule organic matter (cellulose, hemicellulose and lignin etc.), is the coated desirable feedstock of synthetic silicate and then in-situ carbon.
In carbon is coated, the crystallinity of carbon-coating has very important impact to its electric conductivity.Liu Qinglei etc. take rice husk as raw material, adopt transition metal as catalyst, the amorphous carbon based composites with crosslinked carbon nanobelts network is prepared in high-temperature catalytic charing, and have studied its capability of electromagnetic shielding [LiuQL, ZhangD, FanTX, GuJJ, MiyamotoY, ChenZX.Amorphouscarbon-matrixcompositeswithinterconnecte dcarbonnano-ribbonnetworksforelectromagneticinterference shielding.Carbon, 2008,46:461 – 465.].Result shows, the good carbon nanobelts of crystallinity significantly can improve the electric conductivity of material.The purification research of CNT (carbon nano-tube) is shown, the structural stability of amorphous carbon is weaker than the feature of crystallinity charcoal, by 500 DEG C of air oxidations, can significantly except the amorphous carbon in mixed structure material with carbon element, obtain the material with carbon element [BeraD of crystallinity better (conductivity is higher), PerraultJP, HeinrichH, SealS.Defectstudiesonas-synthesizedandpurifiedcarbonnano structuresproducedbyarc-dischargeinsolutionprocess.Journ alofnanoscienceandnanotechnology, 2006, 6:1084-1091.].
Chinese patent application CN103346300A proposition take rice husk as the method for Material synthesis silicate/carbon composite anode material, and in the method, the structure of carbon is amorphous carbon, and conductivity is poor; In addition, the more difficult control of the content of carbon in composite positive pole, thus have impact on the pay(useful) load amount of active material in composite positive pole.
Summary of the invention
For above-mentioned prior art Problems existing and deficiency, the invention provides a kind of method of synthetic silicic acid iron lithium/crystalline carbon composite positive pole.This method improves the crystallinity of carbon in silicate/carbon composite anode material prepared by above-mentioned rice husk, and improves the pay(useful) load of active material in composite material, thus improves the chemical property of material, and the present invention is achieved through the following technical solutions.
A method for synthetic silicic acid iron lithium/crystalline carbon composite positive pole, its concrete steps are as follows:
(1) first the rice husk removing alkali metal oxide impurity will be obtained after rice husk pickling, washing, filtration and drying;
(2) rice husk of removal alkali metal oxide impurity step (1) obtained carries out low temperature pyrogenation and obtains pyrolysis rice husk under anaerobic or aerobic conditions;
(3) pyrolysis rice husk step (2) obtained is that 20 ~ 80:1ml/g joins in the precursor salt solution of transition metal M 1 according to liquid-solid ratio, then high-temperature catalytic carbonization reaction 1h ~ 5h is carried out in anaerobic, temperature under being 700 DEG C ~ 1000 DEG C conditions, obtain catalyzing and carbonizing product, wherein precursor salt solution is solute is transition metal M 1 salt, flux is the solution that water, ethanol or acetone form;
(4) catalyzing and carbonizing product step (3) obtained low-temperature oxidation 0.1h ~ 4h under aerobic, low oxidation temperature are 300 DEG C ~ 600 DEG C conditions obtains oxidation product;
(5) be that 1:1:2 adds source of iron and lithium source and adds water or ethanol wet-milling 3 ~ 20h obtains mixed material according to the silicon dioxide in oxidation product and iron, lithium mol ratio in the oxidation product obtained to step (4), then that mixed material is dry;
(6) be under an inert atmosphere, that 500 ~ 800 DEG C of roasting 1 ~ 20h can prepare silicate/crystalline carbon composite positive pole by step (5) dried mixed material in temperature.
Described rice husk comprises following mass percent component: crude fibre 35.5% ~ 45%, lignin 21% ~ 26%, ash content 11.4% ~ 22%, silica 1 0% ~ 21%, and ash content is silicon dioxide mainly, and all the other are alkali metal oxide.
The acid of the acid cleaning process in described step (1) is HCl, HNO
3or H
2sO
4, its concentration is 5wt% ~ 40wt%, and pickling time is 1h ~ 10h, washs as deionized water washing is until pH is 6 ~ 7.
The condition of the low temperature pyrogenation in described step (2) is: the temperature of pyrolysis is 300 DEG C ~ 600 DEG C, and pyrolysis time is 0.1h ~ 4h.
Transition metal M 1 salt is one or several arbitrary proportion mixtures in iron, cobalt, the nitrate of nickel, acetate, oxalates, chlorate, sulfate in described step (3), and the addition of transition metal M 1 salt is that 0.5 ~ 6:100 adds according to transition metal M 1 and the mass ratio of the pyrolysis rice husk of step (2) gained.
Source of iron is one or several arbitrary proportion mixtures in the oxide of iron, carbonate, acetate, oxalates in described step (5).
Lithium source in described step (5) is one or several arbitrary proportion mixtures in lithium carbonate, lithium acetate, lithia, lithium hydroxide, lithium sulfate, lithium nitrate, lithium phosphate.
Inert atmosphere described in above-mentioned steps (6) is the atmosphere under nitrogen, argon gas, helium or their mist.
The invention has the beneficial effects as follows: (1) this method utilizes cheap agricultural wastes rice husk to be silicon source and carbon source simultaneously, prepares silicate/crystallinity carbon composite anode material, achieves the value added applications of agricultural wastes; (2) this method is by the catalyze of rice husk, forms crystallinity carbon, by the low-temperature oxidation of catalyze rice husk, the amorphous carbon that removing conductivity is poor, control carbon content simultaneously, prepare silicate/crystallinity carbon composite anode material, improve conductivity and the active material load capacity of material.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The method of this synthetic silicic acid iron lithium/crystalline carbon composite positive pole, its concrete steps are as follows:
(1) first will obtain the rice husk removing alkali metal oxide impurity after the pickling of 500g rice husk, washing, filtration and drying, wherein rice husk comprises following mass percent component: crude fibre 45%, lignin 26%, ash content 11.4%, silica 1 0%; The acid of acid cleaning process is HCl, and its concentration is 5wt%, and pickling time is 10h, washs as deionized water washing is until pH is 6 ~ 7;
(2) rice husk of removal alkali metal oxide impurity step (1) obtained carries out low temperature pyrogenation under anaerobic and obtains pyrolysis rice husk, and the temperature of wherein pyrolysis is 600 DEG C, and pyrolysis time is 0.1h;
(3) pyrolysis rice husk step (2) obtained is that 80:1ml/g joins in the precursor salt solution of transition metal M 1 according to liquid-solid ratio, then high-temperature catalytic carbonization reaction 5h is carried out in anaerobic, temperature under being 700 DEG C of conditions, obtain catalyzing and carbonizing product, wherein precursor salt solution is solute is transition metal M 1 salt, flux is the solution that water forms; Transition metal is nitrate and the acetate of quality 1:1 iron, and the addition of transition metal M 1 salt is that 6:100 adds according to transition metal M 1 and the mass ratio of the pyrolysis rice husk of step (2) gained;
(4) catalyzing and carbonizing product step (3) obtained low-temperature oxidation 0.1h under aerobic, low oxidation temperature are 600 DEG C of conditions obtains oxidation product;
(5) be that 1:1:2 adds transition metal source of iron and lithium source and adds ethanol wet-milling 10h and obtains mixed material according to the silicon dioxide in oxidation product and iron, lithium mol ratio in the oxidation product obtained to step (4), then mixed material is dry, wherein source of iron is the oxalates (ferrous oxalate) of iron, and lithium source is lithium carbonate;
(6) under an inert atmosphere, be that 700 DEG C of roasting 15h can prepare silicate/crystalline carbon composite positive pole by step (5) dried mixed material in temperature, inert atmosphere is for pass under 300ml/min condition of nitrogen gas.
Above-mentioned Li2FeSiO4/ crystallinity carbon composite is prepared into battery.Concrete steps are as follows: Li2FeSiO4/ crystallinity carbon composite: conductive agent acetylene black: binding agent PVDF=8:1:1 (mass ratio) mixes, and being uniformly coated on thickness is on the aluminium foil of 20 μm, 80 DEG C of vacuumize 10h, obtained positive plate.Take lithium metal as negative pole, 1MLiPF6 solution (solvent is the EC/EMC of volume ratio 1:1) is electrolyte, barrier film is Celgard2400, is assembled into button cell (CR2025) in argon gas atmosphere glove box.More than the test of LAND battery charging and discharging, carry out charge-discharge test, work system is: constant current charge and discharge, charging and discharging currents 1/16C, charging/discharging voltage are 1.5V ~ 4.8V (vs.Li+/Li).First charge-discharge capacity 140mA/g, be 135mA/g after 20 circulations, capability retention is 96.4%.
Embodiment 2
The method of this synthetic silicic acid iron lithium/crystalline carbon composite positive pole, its concrete steps are as follows:
(1) first will obtain the rice husk removing alkali metal oxide impurity after rice husk pickling, washing, filtration and drying, wherein rice husk comprises following mass percent component: crude fibre 35.5%, lignin 21%, ash 22%, silicon dioxide 21%; The acid of acid cleaning process is HCl, and its concentration is 40wt%, and pickling time is 2h, washs as deionized water washing is until pH is 6 ~ 7;
(2) rice husk of removal alkali metal oxide impurity step (1) obtained carries out low temperature pyrogenation under anaerobic and obtains pyrolysis rice husk, and the temperature of wherein pyrolysis is 400 DEG C, and pyrolysis time is 0.5h;
(3) pyrolysis rice husk step (2) obtained is that 20:1ml/g joins in the precursor salt solution of transition metal M 1 according to liquid-solid ratio, then high-temperature catalytic carbonization reaction 2h is carried out in anaerobic, temperature under being 1000 DEG C of conditions, obtain catalyzing and carbonizing product, the solution that wherein precursor salt solution is solute is transition metal M 1 salt, flux is ethanol composition, nitrate and the acetate of transition metal M 1 salt to be mass ratio be 1:1 iron, the addition of transition metal M 1 salt is that 0.5:100 adds according to transition metal M 1 and the mass ratio of the pyrolysis rice husk of step (2) gained;
(4) catalyzing and carbonizing product step (3) obtained low-temperature oxidation 0.5h under aerobic, low oxidation temperature are 450 DEG C of conditions obtains oxidation product;
(5) be that 1:1:2 adds source of iron and lithium source and adds water wet-milling 10h and obtains mixed material according to the silicon dioxide in oxidation product and iron, lithium mol ratio in the oxidation product obtained to step (4), then mixed material is dry, wherein source of iron is the oxalates (ferrous oxalate) of iron, and lithium source is lithium acetate;
(6) under an inert atmosphere, be that 650 DEG C of roasting 20h can prepare silicate/crystalline carbon composite positive pole by step (5) dried mixed material in temperature, wherein inert atmosphere is pass into the condition of nitrogen gas that flow is 300ml/min.
The chemical property of the method test material identical with embodiment 1.First charge-discharge capacity 138mA/g, be 136.6mA/g after 20 circulations, capability retention is 99%.
Embodiment 3
The method of this synthetic silicic acid iron lithium/crystalline carbon composite positive pole, its concrete steps are as follows:
(1) first will obtain the rice husk removing alkali metal oxide impurity after rice husk pickling, washing, filtration and drying, wherein rice husk comprises following mass percent component: crude fibre 40.3%, lignin 23.5%, ash content 16.7%, silica 1 5.5%; The acid of acid cleaning process is H
2sO
4, its concentration is 20wt%, and pickling time is 9h, washs as deionized water washing is until pH is 6 ~ 7;
(2) rice husk of removal alkali metal oxide impurity step (1) obtained carries out low temperature pyrogenation and obtains pyrolysis rice husk under aerobic conditions; Wherein pyrolysis temperature is 500 DEG C, and pyrolysis time is 1h;
(3) pyrolysis rice husk step (2) obtained is that 50:1ml/g joins in the precursor salt solution of transition metal M 1 according to liquid-solid ratio, then in anaerobic, temperature is carry out high-temperature catalytic carbonization reaction 4h under 900 DEG C of conditions, obtain catalyzing and carbonizing product, wherein precursor salt solution is solute is transition metal M 1 salt, flux is the solution of acetone composition, transition metal salt is the oxalates of the nickel of quality 1:1:1, hydrochloride, sulfate, the addition of transition metal M 1 salt is that 3.3:100 adds according to transition metal M 1 and the mass ratio of the pyrolysis rice husk of step (2) gained,
(4) catalyzing and carbonizing product step (3) obtained low-temperature oxidation 3h under aerobic, low oxidation temperature are 400 DEG C of conditions obtains oxidation product;
(5) be that 1:1:2 adds source of iron and lithium source and adds ethanol wet-milling 10h and obtains mixed material according to the silicon dioxide in oxidation product and iron, lithium mol ratio in the oxidation product obtained to step (4), then mixed material is dry, wherein source of iron is the oxalates (ferrous oxalate) of iron, and lithium source is lithium hydroxide;
(6) under an inert atmosphere, be that 800 DEG C of roasting 10h can prepare silicate/crystalline carbon composite positive pole by step (5) dried mixed material in temperature, wherein inert atmosphere is pass into the helium condition that flow is 300ml/min.
Carry out the Integration Assembly And Checkout of battery according to method identical in embodiment 1, test result: first charge-discharge capacity 150mA/g, be 148mA/g after 20 circulations, capability retention is 98.7%.
Embodiment 4
The method of this synthetic silicic acid iron lithium/crystalline carbon composite positive pole, its concrete steps are as follows:
(1) first the rice husk removing alkali metal oxide impurity will be obtained after rice husk pickling, washing, filtration and drying, wherein rice husk comprises following mass percent component: crude fibre 40.3%, lignin 23.5%, ash content 16.7%, silica 1 5.5%, the acid of acid cleaning process is HNO
3, its concentration is 20wt%, and pickling time is 1h, washs as deionized water washing is until pH is 6 ~ 7;
(2) rice husk of removal alkali metal oxide impurity step (1) obtained carries out low temperature pyrogenation and obtains pyrolysis rice husk under aerobic conditions, and wherein pyrolysis temperature is 300 DEG C, and pyrolysis time is 4h;
(3) pyrolysis rice husk step (2) obtained is that 50:1ml/g joins in the precursor salt solution of transition metal M 1 according to liquid-solid ratio, then high-temperature catalytic carbonization reaction 4h is carried out in anaerobic, temperature under being 950 DEG C of conditions, obtain catalyzing and carbonizing product, the solution that wherein precursor salt solution is solute is transition metal M 1 salt, flux is water composition, transition metal salt is oxalates, chlorate, the nitrate of the cobalt of quality 1:1:1, and the addition of transition metal M 1 salt is that 4:100 adds according to transition metal M 1 and the mass ratio of the pyrolysis rice husk of step (2) gained;
(4) catalyzing and carbonizing product step (3) obtained low-temperature oxidation 1.5h under aerobic, low oxidation temperature are 400 DEG C of conditions obtains oxidation product;
(5) be that 1:1:2 adds source of iron and lithium source and adds ethanol wet-milling 12h and obtains mixed material according to the silicon dioxide in oxidation product and metal M 1, lithium mol ratio in the oxidation product obtained to step (4), then mixed material is dry, wherein transition metal source of iron is the acetate (ferrous acetate) of iron, and lithium source is lithium nitrate;
(6) under an inert atmosphere, be that 720 DEG C of roasting 13h can prepare silicate/crystalline carbon composite positive pole by step (5) dried mixed material in temperature, wherein inert atmosphere is pass into the argon gas condition that flow is 300ml/min.
Carry out the Integration Assembly And Checkout of battery according to method identical in embodiment 1, test result: first charge-discharge capacity 145mA/g, be 143mA/g after 20 circulations, capability retention is 98.6%.
Embodiment 5
The method of this synthetic silicic acid iron lithium/crystalline carbon composite positive pole, its concrete steps are as follows:
(1) first will obtain the rice husk removing alkali metal oxide impurity after rice husk pickling, washing, filtration and drying, wherein rice husk comprises following mass percent component: crude fibre 45%, lignin 26%, ash content 11.4%, silica 1 0%; The acid of acid cleaning process is HCl, and its concentration is 5wt%, and pickling time is 10h, washs as deionized water washing is until pH is 6 ~ 7;
(2) rice husk of removal alkali metal oxide impurity step (1) obtained carries out low temperature pyrogenation and obtains pyrolysis rice husk under aerobic conditions, and the temperature of wherein pyrolysis is 450 DEG C, and pyrolysis time is 2h;
(3) pyrolysis rice husk step (2) obtained is that 50:1ml/g joins in the precursor salt solution of transition metal M 1 according to liquid-solid ratio, then high-temperature catalytic carbonization reaction 1h is carried out in anaerobic, temperature under being 800 DEG C of conditions, obtain catalyzing and carbonizing product, the solution that wherein precursor salt solution is solute is transition metal M 1 salt, flux is ethanol composition, transition metal M 1 salt is the nitrate of iron, and the addition of transition metal M 1 salt is that 5.5:100 adds according to transition metal M 1 and the mass ratio of the pyrolysis rice husk of step (2) gained;
(4) catalyzing and carbonizing product step (3) obtained low-temperature oxidation 2.5h under aerobic, low oxidation temperature are 450 DEG C of conditions obtains oxidation product;
(5) be that 1:1:2 adds source of iron and lithium source and adds water wet-milling 3h and obtains mixed material according to the silicon dioxide in oxidation product and iron, lithium mol ratio in the oxidation product obtained to step (4), then mixed material is dry, wherein source of iron is the oxide (ferrous oxide) of quality 1:1 iron, the mixture of carbonate (ferric carbonate), and lithium source is the lithia of quality 1:1 and the mixture of lithium sulfate;
(6) under an inert atmosphere, be that 500 DEG C of roasting 1h can prepare silicate/crystalline carbon composite positive pole by step (5) dried mixed material in temperature, wherein inert atmosphere is be the nitrogen of 1:1 and the mist condition of argon gas at mass ratio.
Carry out the Integration Assembly And Checkout of battery according to method identical in embodiment 1, test result: first charge-discharge capacity 147mA/g, be 144mA/g after 20 circulations, capability retention is 98.0%.
Embodiment 6
The method of this synthetic silicic acid iron lithium/crystalline carbon composite positive pole, its concrete steps are as follows:
(1) first will obtain the rice husk removing alkali metal oxide impurity after rice husk pickling, washing, filtration and drying, wherein rice husk comprises following mass percent component: crude fibre 35.5%, lignin 21%, ash 22%, silicon dioxide 21%; The acid of acid cleaning process is HCl, and its concentration is 40wt%, and pickling time is 2h, washs as deionized water washing is until pH is 6 ~ 7;
(2) rice husk of removal alkali metal oxide impurity step (1) obtained carries out low temperature pyrogenation and obtains pyrolysis rice husk under aerobic conditions, and the temperature of wherein pyrolysis is 400 DEG C, and pyrolysis time is 3h;
(3) pyrolysis rice husk step (2) obtained is that 50:1ml/g joins in the precursor salt solution of transition metal M 1 according to liquid-solid ratio, then high-temperature catalytic carbonization reaction 1h is carried out in anaerobic, temperature under being 900 DEG C of conditions, obtain catalyzing and carbonizing product, the solution that wherein precursor salt solution is solute is transition metal M 1 salt, flux is acetone composition;
(4) catalyzing and carbonizing product step (3) obtained low-temperature oxidation 2h under aerobic, low oxidation temperature are 300 DEG C of conditions obtains oxidation product;
(5) be that 1:1:2 adds source of iron and lithium source and adds ethanol wet-milling 20h and obtains mixed material according to the silicon dioxide in oxidation product and iron, lithium mol ratio in the oxidation product obtained to step (4), then mixed material is dry, wherein source of iron is the oxalates (ferrous oxalate) of iron, and lithium source is lithium carbonate;
(6) under an inert atmosphere, be that 700 DEG C of roasting 20h can prepare silicate/crystalline carbon composite positive pole by step (5) dried mixed material in temperature, wherein inert atmosphere is under nitrogen atmosphere condition.
Carry out the Integration Assembly And Checkout of battery according to method identical in embodiment 1, test result: first charge-discharge capacity 150mA/g, be 145mA/g after 20 circulations, capability retention is 96.7%.
Claims (7)
1. a method for synthetic silicic acid iron lithium/crystalline carbon composite positive pole, is characterized in that concrete steps are as follows:
(1) first the rice husk removing alkali metal oxide impurity will be obtained after rice husk pickling, washing, filtration and drying;
(2) rice husk of removal alkali metal oxide impurity step (1) obtained carries out low temperature pyrogenation and obtains pyrolysis rice husk under anaerobic or aerobic conditions;
(3) pyrolysis rice husk step (2) obtained is that 20 ~ 80:1mL/g joins in the precursor salt solution of transition metal M 1 according to liquid-solid ratio, then high-temperature catalytic carbonization reaction 1h ~ 5h is carried out in anaerobic, temperature under being 700 DEG C ~ 1000 DEG C conditions, obtain catalyzing and carbonizing product, wherein precursor salt solution is solute is transition metal M 1 salt, solvent is the solution that water, ethanol or acetone form;
(4) catalyzing and carbonizing product step (3) obtained low-temperature oxidation 0.1h ~ 4h under aerobic, low oxidation temperature are 300 DEG C ~ 600 DEG C conditions obtains oxidation product;
(5) be that 1:1:2 adds source of iron and lithium source and adds water or ethanol wet-milling 3 ~ 20h obtains mixed material according to the silicon dioxide in oxidation product and iron, lithium mol ratio in the oxidation product obtained to step (4), then that mixed material is dry;
(6) be under an inert atmosphere, that 500 ~ 800 DEG C of roasting 1 ~ 20h can prepare ferric metasilicate lithium/crystalline carbon composite positive pole by step (5) dried mixed material in temperature;
The condition of the low temperature pyrogenation in described step (2) is: the temperature of pyrolysis is 300 DEG C ~ 600 DEG C, and pyrolysis time is 0.1h ~ 4h.
2. the method for synthetic silicic acid iron lithium/crystalline carbon composite positive pole according to claim 1, is characterized in that: described rice husk comprises following mass percent component: crude fibre 35.5% ~ 45%, lignin 21% ~ 26%, ash content 11.4% ~ 22%.
3. the method for synthetic silicic acid iron lithium/crystalline carbon composite positive pole according to claim 1, is characterized in that: the acid of the acid cleaning process in described step (1) is HCl, HNO
3or H
2sO
4, its concentration is 5wt% ~ 40wt%, and pickling time is 1h ~ 10h, washs as deionized water washing is until pH is 6 ~ 7.
4. the method for synthetic silicic acid iron lithium/crystalline carbon composite positive pole according to claim 1, it is characterized in that: transition metal M 1 salt is one or several arbitrary proportion mixtures in iron, cobalt, the nitrate of nickel, acetate, oxalates, chlorate, sulfate in described step (3), and the addition of transition metal M 1 salt is that 0.5 ~ 6:100 adds according to transition metal M 1 and the mass ratio of the pyrolysis rice husk of step (2) gained.
5. the method for synthetic silicic acid iron lithium/crystalline carbon composite positive pole according to claim 1, is characterized in that: source of iron is one or several arbitrary proportion mixtures in the oxide of iron, carbonate, acetate, oxalates in described step (5).
6. the method for synthetic silicic acid iron lithium/crystalline carbon composite positive pole according to claim 1, is characterized in that: the lithium source in described step (5) is one or several arbitrary proportion mixtures in lithium carbonate, lithium acetate, lithia, lithium hydroxide, lithium sulfate, lithium nitrate, lithium phosphate.
7. the method for synthetic silicic acid iron lithium/crystalline carbon composite positive pole according to claim 2, it is characterized in that: described ash content mainly silicon dioxide, all the other are alkali metal oxide, and wherein dioxide-containing silica is 10% ~ 21% of rice husk quality.
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| CN106531985B (en) * | 2016-10-12 | 2018-07-24 | 深圳市沃特玛电池有限公司 | A kind of preparation method of carbon nanobelts coated LiFePO 4 for lithium ion batteries material |
| CN107658434A (en) * | 2017-06-21 | 2018-02-02 | 吉林大学 | Preparation method, graphite composite material, its preparation method and the application of porous silicon carbon black |
| CN107359325A (en) * | 2017-06-22 | 2017-11-17 | 吉林大学 | The preparation method of carbon coating manganese silicate of lithium composite |
| CN108467047B (en) * | 2018-05-08 | 2019-11-22 | 方嘉城 | A kind of preparation method of ferric metasilicate lithium |
| CN114566619B (en) * | 2021-12-25 | 2023-11-28 | 河南大森林生物科技有限公司 | Green method for preparing lithium ion battery composite anode material by using siliceous biomass |
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| CN103342369A (en) * | 2013-06-08 | 2013-10-09 | 合肥国轩高科动力能源股份公司 | Method for synthesizing silicate cathode material by taking rice husk as raw material |
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