CN103579596B - The preparation method of lithium ion battery negative material - Google Patents

The preparation method of lithium ion battery negative material Download PDF

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CN103579596B
CN103579596B CN201310556327.2A CN201310556327A CN103579596B CN 103579596 B CN103579596 B CN 103579596B CN 201310556327 A CN201310556327 A CN 201310556327A CN 103579596 B CN103579596 B CN 103579596B
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pickling
lithium ion
ion battery
pyrolysis
negative material
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CN103579596A (en
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刘旭
杨续来
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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

Abstract

The invention discloses the preparation method of lithium ion battery negative material; first rice husk is carried out pickling; then it is carried out high temperature pyrolysis; the solid product of acquisition is sufficiently mixed with reducing metal powder; and under inert gas shielding, carry out high temperature reduction reaction; after product carries out pickling, sucking filtration is dried, and obtains consisting of the composite porous of silicon-carbon, and this material can be as the negative material of lithium ion battery.The raw materials used wide material sources of the present invention, with low cost；The porous silicon-carbon obtained has the advantages such as capacity density big, first charge-discharge coulombic efficiency height, good cycle as the negative material of lithium battery.

Description

The preparation method of lithium ion battery negative material
Technical field
The present invention relates to electrode material manufacturing process technology field, particularly relate to a kind of lithium ion battery negative The preparation method of material.
Background technology
Compared with the secondary cell traditional with plumbic acid, NI-G, ni-mh etc., lithium ion battery has running voltage High, volume is little, light weight, capacity density height, memory-less effect, pollution-free, and self discharge is little, The advantage such as have extended cycle life.Nineteen ninety, Sony company of Japan produces first piece of lithium ion battery, lifts Play the commercialization tide of lithium ion battery.
The negative material used in lithium ion battery at present is all material with carbon element, including native graphite, artificial stone Ink and MCMB (MCMB) etc..These Carbon anode have voltage stabilization in charge and discharge process, The advantages such as good cycle.But, the theoretical capacity of graphite material is only 372mAh/g, it is difficult to meet People's pursuit to lithium ion cell high-capacity, the especially electric automobile needs to high-performance lithium battery, An urgent demand exploitation has the negative material of high capacity density.Compared with material with carbon element, the theoretical capacity of silicon is close Degree, up to 4200mAh/g, has bright prospects as Novel anode material.But the embedding/deintercalation at lithium Cheng Zhong, there is serious bulk effect in silicon, material efflorescence is serious, causes capacity attenuation quickly, cyclicity Can be poor.In recent years, research worker has carried out study on the modification to silicon system negative material, receives including to silicon Meter Hua, carbon are coated with and prepare silicon alloy etc., improve the cycle performance of silicon based material to a certain extent. The present invention selects rice husk as the precursor of silicon system negative material, utilizes its pyrolysis solid product to send out with metal powder Raw reduction reaction, forms the silico-carbo composite with loose structure, and this porous material is used as lithium-ion electric The negative pole in pond, has capacity density higher, first the advantage such as coulombic efficiency height and good cycle.
Summary of the invention
The technical problem to be solved in the present invention is to provide the preparation method of a kind of lithium ion battery negative material.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is: lithium ion battery negative material The preparation method of material, comprises the following steps:
1) rice husk is carried out pickling to remove alkali metal impurity therein, be subsequently washed with water to pH and be 6～7, it is dried；
2) to step 1) gained rice husk is pyrolyzed, to decompose lignin therein and cellulose, To pyrolysis solid product；
3) to step 2) dioxide-containing silica in thermal decomposition product detects, according to its content by certain Ratio adds reducing metal powder, mix homogeneously, carries out high temperature reduction reaction under the protection of noble gas；
4) to step 3) gained reduzate first carries out pickling, and being then washed to pH is 6～8, takes out It is filtered dry dry, obtains porous silicon-carbon composite.
As preferably, step 1) in pickling used by acid be HCl or HNO3Or HF or H2SO4, Concentration is 10wt%～40wt%, and pickling time is 2h～4h.
As preferably, step 1) in washing be deionized water wash.
As preferably, step 1) in drying process be 80 DEG C～120 DEG C of oven drying 24h～48h.
As preferably, step 2) condition of described pyrolysis is: pyrolysis protection gas is nitrogen or argon or helium Gas, pyrolysis temperature 500 DEG C～650 DEG C, pyrolysis time is 3h～6h.
As preferably, step 3) in the method for detection silicone content be elemental microanalysis method.
As preferably, step 3) in the mol ratio of reducing metal powder and silicon dioxide be 1.5～2.5.
As preferably, step 3) in reducing metal powder be magnesium powder or aluminium powder or glass putty or iron powder.
As preferably, step 3) in noble gas be nitrogen or argon or helium.
As preferably, step 3) temperature of described high temperature reduction reaction is 800 DEG C～900 DEG C, during reaction Between be 3h～5h.
As preferably, step 4) in pickling be first with the HCl that concentration is 20wt%～40wt% or HNO3Or H2SO4Washing, the HF solution washing of rear 20wt%～40wt%.
By rice husk is carried out a series of process and reaction, obtain the silico-carbo composite wood with loose structure Material.Its preparation technology is simple, easy to operate, and raw material sources are extensive, with low cost；The silico-carbo obtained Composite can be used as the negative pole of lithium ion battery, has capacity density height, good cycle and electrochemistry The preparation of the features such as excellent performance, beneficially high performance lithium ion battery.
Detailed description of the invention
Below by embodiment, the present invention will be further described, but embodiment is not limiting as the protection of the present invention Scope.
Embodiment 1
1) rice husk is soaked in 4h in the HCl solution of 10wt%, carries out pickling to remove alkali therein gold Belong to impurity, be then washed with deionized, sucking filtration 3 times, be 6,80 DEG C of dry 48h to pH；
2) to step 1) gained rice husk under nitrogen protection, 500 DEG C pyrolysis 5h, to decompose wood therein Quality and cellulose, obtain being pyrolyzed solid product；
3) elemental microanalysis method records step 2) molal quantity of silicon dioxide in thermal decomposition product, add magnesium metal Powder, magnesium powder is 2 with the mol ratio of silicon dioxide, and mix homogeneously carries out 800 DEG C under the protection of argon High temperature reduction reaction 4h；
4) to step 3) gained reduzate first carry out 30wt% HCl solution washing, use the most again The HF solution washing of 30wt%, being finally washed with deionized to pH is 7, and sucking filtration 3 times, in 80 DEG C Baking oven is dried 48h, obtains porous silicon-carbon composite.
5) using the porous silicon-carbon composite of preparation as lithium ion battery negative material, and it is carried out charge and discharge Electricity specific capacity and cycle performance test: silico-carbo porous material mixes with conductive agent, binding agent 8:1:1 in mass ratio Making electrode slice as working electrode, lithium metal is as to electrode, and electrolyte is that the mixing of EC and DEC is molten, The volume ratio of the two is 1:1, LiFP6As electrolyte lithium salt, concentration is 1mol/L, and barrier film used is PP (Celgard 2400), assembles button cell in argon gas atmosphere glove box, and make-up electricity carries out charge and discharge electrical measurement Examination, voltage range is 0.01-1.0V (vs.Li+/ Li), electric current density is 0.1C (1C:2000mA/g).
Test result: porous silicon-carbon negative pole material charging and discharging capacity under 0.1C be respectively 724mAh/g, 609mAh/g, coulombic efficiency is 84.2% first, after circulating 200 weeks, charge/discharge capacity be respectively 654mAh/g, 630mAh/g, coulombic efficiency is 96.3%, and capacity attenuation is 9.6%, shows the cycle performance of excellence.
Embodiment 2
1) rice husk is soaked in 3h in the HCl solution of 20wt%, carries out pickling to remove alkali therein gold Belong to impurity, be 7 to pH, be then washed with deionized, sucking filtration 3 times, 100 DEG C of dry 36h；
2) to step 1) gained rice husk is under argon shield, and 550 DEG C of pyrolysis 3h, to decompose wood therein Quality and cellulose, obtain being pyrolyzed solid product；
3) elemental microanalysis method records step 2) molal quantity of silicon dioxide in thermal decomposition product, add metallic aluminium Powder, aluminium powder is 1.5 with the mol ratio of silicon dioxide, and mix homogeneously carries out 850 DEG C under the protection of argon High temperature reduction reaction 3h；
4) to step 3) gained reduzate first carry out 20wt% HCl solution washing, use the most again The HF solution washing of 40wt%, being finally washed with deionized to pH is 7, and sucking filtration 3 times, in 120 DEG C Baking oven is dried 24h, obtains porous silicon-carbon composite.
5) using the porous silicon-carbon composite of preparation as lithium ion battery negative material, and it is carried out charge and discharge Electricity specific capacity and cycle performance test: silico-carbo porous material mixes with conductive agent, binding agent 8:1:1 in mass ratio Making electrode slice as working electrode, lithium metal is as to electrode, and electrolyte is that the mixing of EC and DEC is molten Liquid, the volume ratio of the two is 1:1, LiFP6As electrolyte lithium salt, concentration is 1mol/L, and barrier film used is PP (Celgard 2400), assembles button cell in argon gas atmosphere glove box, and make-up electricity carries out charge and discharge electrical measurement Examination, voltage range is 0.01-1.0V (vs.Li+/ Li), electric current density is 0.1C (1C:2000mA/g).
Test result: porous silicon-carbon negative pole material charging and discharging capacity under 0.1C be respectively 709mAh/g, 583mAh/g, coulombic efficiency is 82.3% first, after circulating 200 weeks, charge/discharge capacity be respectively 638mAh/g, 601mAh/g, coulombic efficiency is 94.2%, and capacity attenuation is 10%, shows the cycle performance of excellence.
Embodiment 3
1) rice husk is soaked in 2h in the HCl solution of 30wt%, carries out pickling to remove alkali therein gold Belong to impurity, be 7 to pH, be then washed with deionized, sucking filtration 3 times, 120 DEG C of dry 24h；
2) to step 1) gained rice husk under nitrogen protection, 600 DEG C pyrolysis 3h, to decompose wood therein Quality and cellulose, obtain being pyrolyzed solid product；
3) elemental microanalysis method records step 2) molal quantity of silicon dioxide in thermal decomposition product, add metallic iron Powder, iron powder is 1.5 with the mol ratio of silicon dioxide, and mix homogeneously carries out 850 DEG C under the protection of argon High temperature reduction reaction 3h；
4) to step 3) gained reduzate first carry out 30wt% HCl solution washing, use the most again The HF solution washing of 30wt%, being finally washed with deionized to pH is 7, and sucking filtration 3 times, in 120 DEG C Baking oven is dried 24h, obtains porous silicon-carbon composite.
5) using the porous silicon-carbon composite of preparation as lithium ion battery negative material, and it is carried out charge and discharge Electricity specific capacity and cycle performance test: silico-carbo porous material mixes with conductive agent, binding agent 8:1:1 in mass ratio Making electrode slice as working electrode, lithium metal is as to electrode, and electrolyte is that the mixing of EC and DEC is molten Liquid, the volume ratio of the two is 1:1, LiFP6As electrolyte lithium salt, concentration is 1mol/L, and barrier film used is PP (Celgard 2400), assembles button cell in argon gas atmosphere glove box, and make-up electricity carries out charge and discharge electrical measurement Examination, voltage range is 0.01-1.0V (vs.Li+/ Li), electric current density is 0.1C (1C:2000mA/g).
Test result: porous silicon-carbon negative pole material charging and discharging capacity under 0.1C be respectively 715mAh/g, 608mAh/g, coulombic efficiency is 85.1% first, after circulating 200 weeks, charge/discharge capacity be respectively 648mAh/g, 615mAh/g, coulombic efficiency is 95%, and capacity attenuation is 9.4%, shows the cycle performance of excellence.
Embodiment 4
1) rice husk is soaked in 2h in the HCl solution of 40wt%, carries out pickling to remove alkali therein gold Belong to impurity, be 6 to pH, be then washed with deionized, sucking filtration 3 times, 120 DEG C of dry 24h；
2) to step 1) gained rice husk under nitrogen protection, 650 DEG C pyrolysis 3h, to decompose wood therein Quality and cellulose, obtain being pyrolyzed solid product；
3) elemental microanalysis method records step 2) molal quantity of silicon dioxide in thermal decomposition product, add metallic tin Powder, glass putty is 2.5 with the mol ratio of silicon dioxide, and mix homogeneously carries out 850 DEG C under the protection of argon High temperature reduction reaction 3h；
4) to step 3) gained reduzate first carry out 20wt% HCl solution washing, use the most again The HF solution washing of 30wt%, being finally washed with deionized to pH is 8, and sucking filtration 3 times, in 120 DEG C Baking oven is dried 24h, obtains porous silicon-carbon composite.
5) using the porous silicon-carbon composite of preparation as lithium ion battery negative material, and it is carried out charge and discharge Electricity specific capacity and cycle performance test: silico-carbo porous material mixes with conductive agent, binding agent 8:1:1 in mass ratio Making electrode slice as working electrode, lithium metal is as to electrode, and electrolyte is that the mixing of EC and DEC is molten Liquid, the volume ratio of the two is 1:1, LiFP6As electrolyte lithium salt, concentration is 1mol/L, and barrier film used is PP (Celgard 2400), assembles button cell in argon gas atmosphere glove box, and make-up electricity carries out charge and discharge electrical measurement Examination, voltage range is 0.01-1.0V (vs.Li+/ Li), electric current density is 0.1C (1C:2000mA/g).
Test result: porous silicon-carbon negative pole material charging and discharging capacity under 0.1C be respectively 698mAh/g, 591mAh/g, coulombic efficiency is 84.7% first, after circulating 200 weeks, charge/discharge capacity be respectively 614mAh/g, 590mAh/g, coulombic efficiency is 96.1%, and capacity attenuation is 12%, shows the cycle performance of excellence.
Embodiment 5
1) rice husk is soaked in 2h in the HCl solution of 30wt%, carries out pickling to remove alkali therein gold Belong to impurity, be 6 to pH, be then washed with deionized, sucking filtration 3 times, 100 DEG C of dry 24h；
2) to step 1) gained rice husk is under argon shield, and 550 DEG C of pyrolysis 3h, to decompose wood therein Quality and cellulose, obtain being pyrolyzed solid product；
3) elemental microanalysis method records step 2) molal quantity of silicon dioxide in thermal decomposition product, add magnesium metal Powder, magnesium powder is 2.5 with the mol ratio of silicon dioxide, and mix homogeneously carries out 800 DEG C under the protection of nitrogen High temperature reduction reaction 3h；
4) to step 3) gained reduzate first carry out 20wt% HCl solution washing, use the most again The HF solution washing of 20wt%, being finally washed with deionized to pH is 7, and sucking filtration 3 times, in 120 DEG C Baking oven is dried 24h, obtains porous silicon-carbon composite.
5) using the porous silicon-carbon composite of preparation as lithium ion battery negative material, and it is carried out charge and discharge Electricity specific capacity and cycle performance test: silico-carbo porous material mixes with conductive agent, binding agent 8:1:1 in mass ratio Making electrode slice as working electrode, lithium metal is as to electrode, and electrolyte is that the mixing of EC and DEC is molten Liquid, the volume ratio of the two is 1:1, LiFP6As electrolyte lithium salt, concentration is 1mol/L, and barrier film used is PP (Celgard 2400), assembles button cell in argon gas atmosphere glove box, and make-up electricity carries out charge and discharge electrical measurement Examination, voltage range is 0.01-1.0V (vs.Li+/ Li), electric current density is 0.1C (1C:2000mA/g).
Test result: porous silicon-carbon negative pole material charging and discharging capacity under 0.1C be respectively 721mAh/g, 585mAh/g, coulombic efficiency is 81.2% first, after circulating 200 weeks, charge/discharge capacity be respectively 645mAh/g, 601mAh/g, coulombic efficiency is close to 93.2%, and capacity attenuation is 10.5%, shows the cycle performance of excellence.
Embodiment 6
1) rice husk is soaked in the H of 20wt%2SO43h in solution, carries out pickling to remove alkali therein Metal impurities, are 7 to pH, are then washed with deionized, sucking filtration 3 times, 80 DEG C of dry 48h；
2) to step 1) gained rice husk under nitrogen protection, 500 DEG C pyrolysis 4h, to decompose wood therein Quality and cellulose, obtain being pyrolyzed solid product；
3) elemental microanalysis method records step 2) molal quantity of silicon dioxide in thermal decomposition product, add magnesium metal Powder, magnesium powder is 2.2 with the mol ratio of silicon dioxide, and mix homogeneously carries out 850 DEG C under the protection of nitrogen High temperature reduction reaction 3h；
4) to step 3) gained reduzate first carries out the H of 20wt%2SO4Solution washs, and uses the most again The HF solution washing of 20wt%, being finally washed with deionized to pH is 8, and sucking filtration 3 times, in 80 DEG C Baking oven is dried 48h, obtains porous silicon-carbon composite.
5) using the porous silicon-carbon composite of preparation as lithium ion battery negative material, and it is carried out charge and discharge Electricity specific capacity and cycle performance test: silico-carbo porous material mixes with conductive agent, binding agent 8:1:1 in mass ratio Making electrode slice as working electrode, lithium metal is as to electrode, and electrolyte is that the mixing of EC and DEC is molten Liquid, the volume ratio of the two is 1:1, LiFP6As electrolyte lithium salt, concentration is 1mol/L, and barrier film used is PP (Celgard 2400), assembles button cell in argon gas atmosphere glove box, and make-up electricity carries out charge and discharge electrical measurement Examination, voltage range is 0.01-1.0V (vs.Li+/ Li), electric current density is 0.1C (1C:2000mA/g).
Test result: porous silicon-carbon negative pole material charging and discharging capacity under 0.1C be respectively 714mAh/g, 576mAh/g, coulombic efficiency is 80.7% first, after circulating 200 weeks, charge/discharge capacity be respectively 633mAh/g, 599mAh/g, coulombic efficiency is 94.6%, and capacity attenuation is 11.3%, shows the cycle performance of excellence.
Above-described embodiment is only example character.For those skilled in the art, it is possible to understand that without departing from These embodiments can be carried out in the case of the principle of the present invention and spirit multiple change, revise, replace and Degeneration, the scope of the present invention claims again and equivalent thereof limit.

Claims (10)

1. the preparation method of a lithium ion battery negative material, it is characterised in that comprise the following steps:
1) rice husk carrying out pickling to remove alkali metal impurity therein, being subsequently washed with water to pH is 6～7, is dried；
2) to step 1) gained rice husk is pyrolyzed, to decompose lignin therein and cellulose, obtains being pyrolyzed solid product；
3) to step 2) dioxide-containing silica in thermal decomposition product detects, adds reducing metal powder, mix homogeneously by a certain percentage according to its content, carry out high temperature reduction reaction under the protection of noble gas；
4) to step 3) gained reduzate first carries out pickling, and being then washed to pH is 6～8, and sucking filtration is dried, and obtains porous silicon-carbon composite.
2. as claimed in claim 1 method, it is characterised in that: step 1) in pickling used by acid be HCl or HNO3Or HF or H2SO4, concentration is 10wt%～40wt%, and pickling time is 2h～4h, and washing is then deionized water wash.
3. as claimed in claim 1 method, it is characterised in that: step 1) in drying process be 80 DEG C～120 DEG C of oven drying 24h～48h.
4. as claimed in claim 1 method, it is characterised in that: step 2) condition of described pyrolysis is: pyrolysis protection gas is nitrogen or argon or helium, and pyrolysis temperature 500 DEG C～650 DEG C, pyrolysis time is 3h～6h.
5. as claimed in claim 1 method, it is characterised in that: step 3) in the method for detection silicone content be elemental microanalysis method.
6. as claimed in claim 1 method, it is characterised in that: step 3) in the mol ratio of reducing metal powder and silicon dioxide be 1.5～2.5.
7. as claimed in claim 1 method, it is characterised in that: step 3) in reducing metal powder be magnesium powder or aluminium powder or glass putty or iron powder.
8. as claimed in claim 1 method, it is characterised in that: step 3) in noble gas be nitrogen or argon or helium.
9. as claimed in claim 1 method, it is characterised in that: step 3) temperature of described high temperature reduction reaction is 800 DEG C～900 DEG C, the response time is 3h～5h.
10. as claimed in claim 1 method, it is characterised in that: step 4) in pickling be first with HCl or HNO that concentration is 20wt%～40wt%3Or H2SO4Washing, the HF solution washing of rear 20wt%～40wt%.
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