CN107068993B - A kind of compound Co of three-dimensional3O4The preparation method of-Si-C negative electrode material - Google Patents
A kind of compound Co of three-dimensional3O4The preparation method of-Si-C negative electrode material 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
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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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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- 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
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Abstract
The invention discloses a kind of compound Co of three-dimensional3O4The preparation method of-Si-C negative electrode material, method includes the following steps: (1) regard nickel foam as conductive current collector after low-kappa number；(2) by acid, treated that nickel foam is transferred in the reaction kettle of the mixed aqueous solution equipped with cobalt nitrate, urea and ammonium fluoride, heats reaction kettle, and constant temperature is for a period of time, is then cooled to room temperature, Co is made through high-temperature calcination after product washing is dry3O4Nanowire structure array；(3) soluble silicon source is dissolved in ion liquid system, using product made from above-mentioned steps (2) as cathode, using inertia electricity grade as anode, constant pressure or constant current electro-deposition are carried out at a certain temperature, and electro-deposition product isolates ionic liquid by organic matter cleaning and obtains silicon layer；(4) spray C Surface processing is carried out with product prepared by above-mentioned steps (3).
Description
Technical field
The invention belongs to battery technology fields, and in particular to a kind of compound Co of three-dimensional3O4The preparation side of-Si-C negative electrode material
Method, in particular to a kind of ionic liquid are the method that electrolyte is electrolysed Si layers of preparation cathode material of lithium ion battery.
Background technique
Energy and material is that the mankind are able to booming foundation stone, and progress runs through the advance of entire society, science and technology, economy.
With social progress, the increase in demand of traditional energy petered out with people to the renewable sources of energy, carries out new energy materials and grind
Hair has become one of the important topic of the mankind now.Basically, most important factor be it is for the survival of mankind can not be again
Raw energy resources are increasingly in short supply and problem of environmental pollution becomes increasingly conspicuous, such as global warming, haze, acid rain environment are asked
Topic, therefore people have to actively or passively find new energy conversion and storage device.Battery material is as new energy materials
One kind, the advantages such as energy density with higher, mobility are preferable, output voltage stabilization, and working environment is mild, in people
Daily life and scientific research, industrial circle be used widely, for example as laptop, mobile phone, camera power supply, and
The power of various industry handheld devices, or even the power supply initially as large-scale plant.In many batteries, lithium ion battery with it is other
Battery is compared, and has high voltage, high-energy-density, high charge-discharge rate, low self-discharge rate, good charge discharge life, subenvironment
The advantages that pollution.Lithium ion battery gradually gets the mastery from the competition with other novel batteries and takes the lead in popularizing at present,
Start instead of nickel-metal hydride battery, nickel-cadmium cell, traditional status of lead-acid battery.However, between nearest 20 years lithium battery industry
Change progress to start to go no further, the energy density of unit mass and unit volume increasess slowly, this is relative to present industry, section
Skill, amusement fast development extremely lag.Therefore, research and development high-energy density, long-life, high-power lithium battery very must
It wants.
The chemical property of lithium ion secondary battery is highly dependent on its building block, especially positive and negative anodes electrode material
Composition, structure and property have decisive role to overall performance.Therefore, it in order to further increase performance, needs around some bases
Corresponding improvement is furtherd investigate and then is found in plinth project, for example synthesis, preparation and its physicochemical properties of battery electrode material
With solution.Being actually used in the negative electrode material of lithium ion battery at present is essentially all carbon materials, such as electrographite.
400mAhg is generally not more than in the specific capacity of the carbon material of research-1, since irreversible loss for the first time is big, multiplying power discharging property
Difference etc., assembled battery has been far from satisfying actual demand.Lithium ion battery negative material is the key that lithium ion battery group
At part, therefore develops Novel high-specific capacity flexible lithium ion battery negative material and decision is played to the further development of lithium ion battery
Effect.
Silicon is expected to replace graphite cathode in business application, its attraction is originated from its theoretical appearance for being up to 4200mAh/g
Amount, ABUNDANT NATUREAL RESOURSES and low-work voltage.But Si is in Li+It can be along with huge volume expansion during intercalation/deintercalation
(~400%), and generate huge stress.These stress can cause the crushing of Si and thereby cause to be detached from its collector,
The final irreversible decaying that capacity occurs.In addition, organic electrolyte is easy to decompose reaction in electrode surface, in the surface Si shape
At one layer of SEI film.Violent volume expansion and contraction will lead to its cracking, it is difficult to stablize.This exposes the surface Si again to the open air
SEI is formed in electrolyte again, eventually leads in charge and discharge process that SEI film is more and more thicker, is unfavorable for the fortune of lithium ion and electronics
It is defeated, finally influence cycle performance.Therefore, composite nanostructure can be synthesized by design, to overcome Si in charge and discharge process
The shortcomings that volume expansion, the coulombic efficiency and cyclical stability of material are improved, to prepare ideal electrode.Currently, existing
A large amount of research is concentrated on using carbon nanotube and graphite as conductive substrates, the volume of Lai Rongna active electrode material in the circulating cycle
Variation.In short, researcher such as prepares Si nanostructure, the Si/ Metals composite of different-shape by the design of pattern or structure
Material or Si/C composite material, are remarkably improved the chemical property of Si base negative electrode material.
Summary of the invention
The present invention is prepared for Co using means such as hydro-thermal reaction and electro-deposition for the first time3O4- Si-C composite material, creative utilization
Ionic liquid is electrolyte electro-deposition Si nano particle, rather than traditional sol-gel-reducing process.Structure effective use
The advantages of materials such as cobalt oxide, silicon, carbon, makes it have greater advantage than conventional oxidation cobalt nanowire.In composite material, C
The aggregation and transmission that there is clad high conductivity to be conducive to charge.The introducing of Si not only substantially increases specific capacity, Er Qiewu
The Si of sizing is unstable, and surface is easy to generate one layer of SiO2, certain effect is played to the volume change for inhibiting Si.Preparation
Co3O4- Si-C composite material has excellent chemical property.
A kind of compound Co of three-dimensional of the present invention3O4The preparation method of-Si-C negative electrode material, comprising the following steps:
(1) nickel foam is used as to conductive current collector after low-kappa number；
(2) by the reaction of acid treated nickel foam the is transferred to mixed aqueous solution equipped with cobalt nitrate, urea and ammonium fluoride
In kettle, reaction kettle is heated, and constant temperature is for a period of time, is then cooled to room temperature, is made after product washing is dry through high-temperature calcination
Co3O4Nanowire structure array；
(3) soluble silicon source is dissolved in ion liquid system, it is lazy using product made from above-mentioned steps (2) as cathode
Property electrolyte be anode, carry out constant pressure or constant current electro-deposition at a certain temperature, electro-deposition product is by organic matter cleaning separation
Ionic liquid obtains silicon layer out；
(4) spray C Surface processing is carried out with product prepared by above-mentioned steps (3).
Further, low-kappa number described in step (1) is that nickel foam is impregnated 5min in 30% concentrated nitric acid, it is therefore an objective to
Remove the oxide layer on surface.
Further, mixed aqueous solution described in step (2) is by 1.0-3.0g cobalt nitrate, 0.3-0.5g ammonium fluoride and 1.0-
3.0 g urea are dissolved in 50mL distilled water, are slowly stirred about 30 minutes.Entire mixed solution is moved into inner liner polytetrafluoroethylene
Autoclave in, the nickel foam cut is put into tetrafluoroethene, reaction solution loading 80%, at a certain temperature
(120 DEG C) reaction 1-5h.After reaction, it is waited to be cooled to room temperature range, is then alternately cleaned three times with deionized water and ethyl alcohol
To remove impurity, 12h then is handled in the drying box at 80 DEG C.High-temperature roasting 3h under the conditions of 350-450 DEG C last, obtains institute
Need product.
Further, by the Co of the direct growth nickel foam prepared in step (3)3O4Nano-array is as cathode, Pt net electricity
Contain 0.25M SiCl as inert anode, at 50 DEG C in pole4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage -2.4V,
Time is 1-5 hours, and electro-deposition product cleaning solution is organic solvent-acetone, obtains elemental silicon after washing.
According to above-mentioned preparation method, wherein step (4) the middle use KYKY SBC-2 surface treating machine carries out spray carbon
Processing coats C layers on the surface of the material, and the method is simple and facilitates.
The positive effect of the present invention is: using nickel foam with good conductivity as substrate, nickel foam has big ratio table
Area, the addition that the quality of active material can be improved, and eliminate binder and conductive black etc., to improve the conduction of material
Property, Si has the up to advantages such as theoretical specific capacity, ABUNDANT NATUREAL RESOURSES and low-work voltage of 4200mAh/g, utilizes ionic liquid
For electrolyte electro-deposition Si nano particle, rather than traditional sol-gel-reducing process.The structure is effectively utilized oxidation
The advantages of materials such as cobalt, silicon, carbon, makes it have greater advantage than conventional oxidation cobalt nanowire.In composite material, C clad
Be conducive to the aggregation and transmission of charge with high conductivity.The introducing of Si not only substantially increases specific capacity, but also surface is easy
Generate one layer of SiO2, certain effect is played to the volume change for inhibiting Si.
Detailed description of the invention
Fig. 1 is the schematic diagram of preparation method of the present invention.
Fig. 2 is the scanning electron microscope diagram in embodiment 1 after treated nickel foam hydro-thermal reaction 5h.
Fig. 3 is that the scanning electron microscope diagram that the Si time is 2h is electrolysed in embodiment 1.
Fig. 4 is final Co in case study on implementation 13O4The Raman spectrogram of-Si-C composite material.
Specific embodiment
Technical solution of the present invention is further illustrated below in conjunction with drawings and examples, but following embodiment only has explanation
Property, and the scope of protection of the present invention is not limited.
In battery performance test result, nano combined Co is found3O4- Si-C negative electrode material and simple Co3O4Cathode material
Material is compared to higher specific capacity value and good cycle performance.
Embodiment 1
Nickel foam is impregnated into 5min in 30% concentrated nitric acid first, removes the oxide layer on surface, then by the Co of 1.46g
(NO3)2 6H2The NH of O, 0.37g4CO (the NH of F and 1.5g2)2It is dissolved in 50 milliliters of distilled water, entire adition process is in magnetic force
Stirring is lower to be carried out.After stirring 30 minutes, entire mixed solution is moved into the autoclave of inner liner polytetrafluoroethylene, will be cut
The nickel foam crossed is put into tetrafluoroethene, reaction solution loading 80%, reacts 5h at a temperature of 120 DEG C.After reaction, it is waited
It is cooled to room temperature range, then alternately cleaning is three times to remove impurity with deionized water and ethyl alcohol, the then drying at 80 DEG C
12h is handled in case.High-temperature roasting 3h under the conditions of last 450 DEG C, obtains required product.Soluble silicon source is dissolved in ionic liquid
In system, by the Co of the direct growth nickel foam prepared3O4Nano-array as cathode, Pt net electrode as inert anode,
50 DEG C contain 0.25M SiCl4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage -2.4V, the time is 2 hours, and electricity is heavy
Product product cleaning solution is organic solvent-acetone, obtains elemental silicon after washing.By the Co of above-mentioned preparation3O4- Si is placed on KYKY
SBC-2 surface treating machine instrument carries out spray carbon processing.Fig. 2 is sweeping after treated nickel foam hydro-thermal reaction 5h in embodiment 1
Retouch electron microscope picture.It can obviously observe the formation of nano array structure.Fig. 3 be in embodiment 1 be electrolysed the Si time be 2h
Scanning electron microscope diagram, show that nanowire surface becomes coarse from figure.
Embodiment 2
Nickel foam is impregnated into 5min in 30% concentrated nitric acid first, removes the oxide layer on surface, then by the Co of 1.46g
(NO3)2 6H2The NH of O, 0.37g4CO (the NH of F and 1.5g2)2It is dissolved in 50 milliliters of distilled water, entire adition process is in magnetic force
Stirring is lower to be carried out.After stirring 30 minutes, entire mixed solution is moved into the autoclave of inner liner polytetrafluoroethylene, will be cut
The nickel foam crossed is put into tetrafluoroethene, reaction solution loading 80%, at a certain temperature (120 DEG C) reaction 5h.After reaction,
It is waited to be cooled to room temperature range, then alternately cleaning is three times to remove impurity with deionized water and ethyl alcohol, then at 80 DEG C
Drying box in handle 12h.High-temperature roasting 3h under the conditions of last 450 DEG C, obtains required product.By soluble silicon source be dissolved in from
It, will be with the Co of the direct growth nickel foam of preparation in sub- liquid system3O4Nano-array is as cathode, and Pt net electrode is as inertia
Anode, 50 DEG C contain 0.25M SiCl4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage -2.4V, electrolysis time changes
For 5h, electro-deposition product cleaning solution is organic solvent-acetone, obtains elemental silicon after washing.By the Co of above-mentioned preparation3O4- Si is put
Spray carbon processing is carried out in KYKY SBC-2 surface treating machine instrument.
Embodiment 3
Nickel foam is impregnated into 5min in 30% concentrated nitric acid first, removes the oxide layer on surface, then by the Co of 1.46g
(NO3)2 6H2The NH of O, 0.37g4CO (the NH of F and 1.5g2)2It is dissolved in 50 milliliters of distilled water, entire adition process is in magnetic force
Stirring is lower to be carried out.After stirring 30 minutes, entire mixed solution is moved into the autoclave of inner liner polytetrafluoroethylene, will be cut
The nickel foam crossed is put into tetrafluoroethene, reaction solution loading 80%, at a certain temperature (120 DEG C) reaction 5h.After reaction,
It is waited to be cooled to room temperature range, then alternately cleaning is three times to remove impurity with deionized water and ethyl alcohol, then at 80 DEG C
Drying box in handle 12h.High-temperature roasting 3h under the conditions of last 450 DEG C, obtains required product.By soluble silicon source be dissolved in from
It, will be with the Co of the direct growth nickel foam of preparation in sub- liquid system3O4Nano-array is as cathode, and Pt net electrode is as inertia
Anode, 50 DEG C contain 0.25M SiCl4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage -2.6V, electrolysis time
2h, electro-deposition product cleaning solution are organic solvent-acetone, obtain elemental silicon after washing.By the Co of above-mentioned preparation3O4- Si is placed on
KYKY SBC-2 surface treating machine instrument carries out spray carbon processing.
It describes the invention in detail above, it is clear that as long as essentially without inventive point and effect of the invention is detached from
Fruit, obvious variations to those skilled in the art, are also all included in the scope of protection of the present invention.
Claims (7)
1. a kind of compound Co of three-dimensional3O4The preparation method of-Si-C negative electrode material, which is characterized in that include the following steps
(1) nickel foam is used as to conductive current collector after low-kappa number；
(2) by acid, treated that nickel foam is transferred in the reaction kettle of the mixed aqueous solution equipped with cobalt nitrate, urea and ammonium fluoride,
Reaction kettle is heated, and constant temperature is for a period of time, is then cooled to room temperature, Co is made through high-temperature roasting after product washing is dry3O4Receive
Nanowire structure array；
(3) soluble silicon source is dissolved in ion liquid system, using product made from above-mentioned steps (2) as cathode, with inertia
Electric grade is anode, carries out constant pressure or constant current electro-deposition at a certain temperature, electro-deposition product by organic matter cleaning isolate from
Sub- liquid obtains silicon layer；
(4) spray C Surface processing is carried out with product prepared by above-mentioned steps (3).
2. method according to claim 1, which is characterized in that low-kappa number described in step (1) is by nickel foam 30%
Concentrated nitric acid in impregnate 5min.
3. method according to claim 1, which is characterized in that mixed aqueous solution described in step (2) is by 1.0-3.0g nitre
Sour cobalt, 0.3-0.5g ammonium fluoride and 1.0-3.0g urea are dissolved in 50mL distilled water, stir 30 minutes gained.
4. method according to claim 1, which is characterized in that reaction kettle described in step (2) is inner liner polytetrafluoroethylene
Autoclave.
5. method according to claim 1, which is characterized in that heating reaction kettle described in step (2) is carried out instead at 120 DEG C
1-5h is answered, product roasts 3h under the conditions of 350-450 DEG C.
6. method according to claim 1, which is characterized in that electro-deposition product described in step (3) is contained at 50 DEG C
0.25M SiCl4Quaternary ammonium salt ionic liquid in silicon electrolyzation obtain.
7. method according to claim 1, which is characterized in that the processing of spray C Surface described in step (4) is using KYKY
SBC-2 surface treating machine carries out spray carbon processing, coats C layers on the surface of the material.
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| CN108982609A (en) * | 2018-06-19 | 2018-12-11 | 中国科学院合肥物质科学研究院 | A kind of three-dimensional carbon cloth/ferronickel layered hydroxide cladding cobaltosic oxide nano line composite material and preparation method and application |
| CN108615620B (en) * | 2018-06-20 | 2020-09-22 | 华南理工大学 | Carbon nano tube/metal sulfide composite electrode with foamed nickel as substrate and preparation method thereof |
| CN108593729A (en) * | 2018-06-27 | 2018-09-28 | 中山大学 | A kind of preparation method of the porous golden blood glucose micropin electrochemical sensor module of no proteins carry enzyme |
| CN109524640B (en) * | 2018-10-19 | 2021-04-20 | 西安科技大学 | Flexible self-supporting lithium ion battery cathode material and preparation method thereof |
| CN110931769B (en) * | 2019-11-27 | 2022-09-02 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of foamed nickel in-situ growth ternary cathode material, product and application |
| CN114156454A (en) * | 2021-12-02 | 2022-03-08 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of three-dimensional core-shell nanoflower array material, product and application thereof |
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