CN107068993A - A kind of three-dimensional compound Co3O4The preparation method of Si C negative materials - Google Patents

A kind of three-dimensional compound Co3O4The preparation method of Si C negative materials Download PDF

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CN107068993A
CN107068993A CN201710031319.4A CN201710031319A CN107068993A CN 107068993 A CN107068993 A CN 107068993A CN 201710031319 A CN201710031319 A CN 201710031319A CN 107068993 A CN107068993 A CN 107068993A
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nickel foam
deposition
electro
temperature
constant
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CN107068993B (en
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刘莉丽
杜长江
刘春辉
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Beijing Technology and Business University
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/38Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386Silicon or alloys based on silicon
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M2004/026Electrodes composed of or comprising active material characterised by the polarity
    • H01M2004/027Negative electrodes
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a kind of three-dimensional compound Co3O4The preparation method of Si C negative materials, this method comprises the following steps:(1) it regard nickel foam as conductive current collector after low-kappa number;(2) nickel foam after acid treatment is transferred in the reactor of the mixed aqueous solution equipped with cobalt nitrate, urea and ammonium fluoride, heating response kettle, and constant temperature is for a period of time, is then cooled to room temperature, Co is made through high-temperature calcination after drying in product washing3O4Nano thread structure array;(3) soluble silicon source is dissolved in ion liquid system, using product made from above-mentioned steps (2) as negative electrode, using the electric level of inertia 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) product prepared with above-mentioned steps (3) carries out spray C Surface processing.

Description

A kind of three-dimensional compound Co3O4The preparation method of-Si-C negative materials
Technical field
The invention belongs to cell art, and in particular to a kind of three-dimensional compound Co3O4The preparation side of-Si-C negative materials Method, more particularly to a kind of ionic liquid is the method that electrolyte is electrolysed Si layers of preparation cathode material of lithium ion battery.
Background technology
Energy and material is that the mankind are able to booming foundation stone, and it improves through entire society, science and technology, economic advance. With social progress, the increase in demand petered out with people to the renewable sources of energy of traditional energy, carry out new energy materialses and grind Hair turns into one of 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 worsening shortages, and problem of environmental pollution are become increasingly conspicuous, and such as global warming, haze, acid rain environment are asked Inscribe, therefore people have to actively or passively find novel energy conversion and storage device.Battery material is used as new energy materialses One kind, with higher energy density, mobility preferably, output voltage stabilization, the advantage such as working environment is gentle, in people Daily life and scientific research, industrial circle be used widely, for example as notebook computer, mobile phone, camera power supply, and The power of various industrial handheld devices, or even initially as the power supply of large-scale plant.In many batteries, lithium ion battery with it is other Battery is compared, with high voltage, high-energy-density, high charge-discharge speed, low self-discharge rate, good charge and discharge electric life, subenvironment The advantages of pollution.Current lithium ion battery gradually gets the mastery and the popularization that takes the lead in from the competition with other novel batteries, Start to instead of Ni-MH 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, the fast development of amusement are very delayed.Therefore, research and development high-energy-density, long-life, high-power lithium battery very must Will.
The chemical property of lithium rechargeable battery is highly dependent on its building block, particularly both positive and negative polarity electrode material Composition, structure and property have decisive role to overall performance.Therefore, in order to further improve performance, it is necessary to surround some bases Synthesis, preparation and its physicochemical properties of plinth problem, for example battery electrode material, further investigate and then find corresponding improvement With solution.The negative material for being actually used in 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, because irreversible loss first is big, multiplying power discharging property Difference etc., its assembled battery far can not meet actual demand.Lithium ion battery negative material is crucial group of lithium ion battery Into part, therefore further development of the exploitation Novel high-specific capacity flexible lithium ion battery negative material to lithium ion battery plays decision Effect.
Silicon is expected in business application replace graphite cathode, and its attraction is derived from the theoretical appearance that it is up to 4200mAh/g Amount, ABUNDANT NATUREAL RESOURSES and low-work voltage.But, Si is in Li+Can be along with huge volumetric expansion during intercalation/deintercalation (~400%), and produce huge stress.These stress can cause Si crushing and thereby cause to depart from its collector, The final irreversible decay for occurring capacity.In addition, organic electrolyte is easy to decompose reaction in electrode surface, in Si surfaces shape Into one layer of SEI film.Violent volumetric expansion and contraction can cause it to ftracture, it is difficult to stable.This causes Si surfaces to expose to the open air again SEI is formed in electrolyte again, ultimately results in charge and discharge process that SEI films are more and more thicker, is unfavorable for the fortune of lithium ion and electronics It is defeated, finally influence cycle performance.It therefore, it can by designing synthesis composite nanostructure, to overcome Si in charge and discharge process The shortcoming of volumetric expansion, improves the coulombic efficiency and cyclical stability of material, so as to prepare preferable electrode.At present, it is existing Substantial amounts of research is concentrated on using CNT and graphite as conductive substrates, to accommodate the volume of active electrode material in the circulating cycle Change.In a word, researcher such as prepares Si nanostructureds, the Si/ Metals composites of different-shape by the design of pattern or structure Material or Si/C composites, are remarkably improved the chemical property of Si base negative materials.
The content of the invention
The present invention is prepared for Co using means such as hydro-thermal reaction and electro-deposition first3O4- Si-C composites, creative utilization Ionic liquid is electrolyte electro-deposition Si nano particles, rather than traditional sol-gel-reducing process.The structure is effectively utilized The advantage of the materials such as cobalt oxide, silicon, carbon, makes it possess greater advantage than conventional oxidation cobalt nanowire.In composite, C There is clad high conductivity to be conducive to the aggregation and transmission of electric charge.Si introducing not only substantially increases specific capacity, Er Qiewu The Si of sizing is unstable, and surface easily generates one layer of SiO2, certain effect is played to the Volume Changes for suppressing Si.Prepare Co3O4- Si-C composites have excellent chemical property.
A kind of three-dimensional compound Co of the invention3O4The preparation method of-Si-C negative materials, comprises the following steps:
(1) it regard nickel foam as conductive current collector after low-kappa number;
(2) nickel foam after acid treatment is transferred to the reaction of the mixed aqueous solution equipped with cobalt nitrate, urea and ammonium fluoride In kettle, heating response kettle, and constant temperature is for a period of time, is then cooled to room temperature, product washing is made after drying through high-temperature calcination Co3O4Nano thread structure array;
(3) soluble silicon source is dissolved in ion liquid system, it is lazy as negative electrode using product made from above-mentioned steps (2) Property electrolyte be anode, constant pressure or constant current electro-deposition are carried out at a certain temperature, electro-deposition product cleans separation by organic matter Go out ionic liquid and obtain silicon layer;
(4) product prepared with above-mentioned steps (3) carries out spray C Surface processing.
Further, low-kappa number described in step (1) is that nickel foam is soaked into 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 nitrates, 0.3-0.5g ammonium fluorides and 1.0- 3.0g urea is dissolved in 50mL distilled water, is slowly stirred about 30 minutes.Whole 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 scope, then with alternately cleaning three times of deionized water and ethanol To go the removal of impurity, then 12h is handled in the drying box at 80 DEG C.High-temperature roasting 3h under the conditions of last 350-450 DEG C, obtains institute Need product.
Further, by the Co of the direct growth nickel foam prepared in step (3)3O4Nano-array is used as negative electrode, Pt net electricity Contain 0.25M SiCl at 50 DEG C as inert anode 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, and elemental silicon is obtained after washing.
According to above-mentioned preparation method, wherein step (4) the middle use KYKY SBC-2 surface treating machines carry out spray carbon Processing, C layers are coated in material surface, 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, can improve the quality of active material, and eliminate the addition of binding agent and conductive black etc., so as to improve the conduction of material Property, Si has the up to advantage such as 4200mAh/g theoretical specific capacity, ABUNDANT NATUREAL RESOURSES and low-work voltage, utilizes ionic liquid For electrolyte electro-deposition Si nano particles, rather than traditional sol-gel-reducing process.The structure is effectively utilized oxidation The advantage of the materials such as cobalt, silicon, carbon, makes it possess greater advantage than conventional oxidation cobalt nanowire.In composite, C clads Be conducive to the aggregation and transmission of electric charge with high conductivity.Si introducing not only substantially increases specific capacity, and surface is easy Generate one layer of SiO2, certain effect is played to the Volume Changes for suppressing Si.
Brief description of the drawings
Fig. 1 is the schematic diagram of preparation method of the present invention.
Fig. 2 is the scanning electron microscope diagram after the nickel foam hydro-thermal reaction 5h after being handled in embodiment 1.
Fig. 3 is the scanning electron microscope diagram that the electrolysis Si times are 2h in embodiment 1.
Fig. 4 is final Co in case study on implementation 13O4The Raman spectrogram of-Si-C composites.
Embodiment
Technical scheme is further illustrated below in conjunction with drawings and examples, but following examples only have explanation Property, do not limit protection scope of the present invention.
In battery performance test result, nano combined Co is found3O4- Si-C negative materials and simple Co3O4Negative pole material Material, which is compared, has higher specific capacity value and good cycle performance.
Embodiment 1
Nickel foam is soaked into 5min in 30% concentrated nitric acid first, the oxide layer on surface is removed, then by 1.46g Co (NO3)26H2O, 0.37g NH4F and 1.5g CO (NH2)2It is dissolved in 50 milliliters of distilled water, whole adition process is stirred in magnetic force Mix lower progress.After stirring 30 minutes, in the autoclave that whole mixed solution is moved into inner liner polytetrafluoroethylene, it will cut Nickel foam be put into tetrafluoroethene, reaction solution loading 80% reacts 5h at a temperature of 120 DEG C.After reaction, wait its cold But room temperature scope is arrived, then three times are alternately cleaned with deionized water and ethanol to go the removal of impurity, then the drying box at 80 DEG C Middle processing 12h.High-temperature roasting 3h under the conditions of last 450 DEG C, obtains required product.Soluble silicon source is dissolved in ionic liquid body In system, by the Co of the direct growth nickel foam prepared3O4Nano-array is as negative electrode, and Pt nets electrode is as inert anode, 50 DEG C contain 0.25M SiCl4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage -2.4V, the time be 2 hours, electro-deposition Product cleaning solution is organic solvent-acetone, and elemental silicon is obtained 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 the scanning electron after the nickel foam hydro-thermal reaction 5h after being handled in embodiment 1 Microscope figure.The formation of nano array structure can substantially be observed.Fig. 3 is the scanning that the electrolysis Si times are 2h in embodiment 1 Electron microscope picture, shows that nanowire surface becomes coarse from figure.
Embodiment 2
Nickel foam is soaked into 5min in 30% concentrated nitric acid first, the oxide layer on surface is removed, then by 1.46g Co (NO3)26H2O, 0.37g NH4F and 1.5g CO (NH2)2It is dissolved in 50 milliliters of distilled water, whole adition process is stirred in magnetic force Mix lower progress.After stirring 30 minutes, in the autoclave that whole mixed solution is moved into inner liner polytetrafluoroethylene, it will cut Nickel foam be put into tetrafluoroethene, reaction solution loading 80%, at a certain temperature (120 DEG C) reaction 5h.After reaction, etc. Treat that it is cooled to room temperature scope, then three times are alternately cleaned with deionized water and ethanol to go the removal of impurity, then at 80 DEG C 12h is handled in drying box.High-temperature roasting 3h under the conditions of last 450 DEG C, obtains required product.Soluble silicon source is dissolved in ion In liquid system, by with the Co of the direct growth nickel foam of preparation3O4Nano-array is used as inertia sun as negative electrode, Pt nets electrode Pole, contains 0.25M SiCl at 50 DEG C4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage -2.4V, electrolysis time is changed to 5h, electro-deposition product cleaning solution is organic solvent-acetone, and elemental silicon is obtained after washing.By the Co of above-mentioned preparation3O4- Si is placed on KYKY SBC-2 surface treating machines instrument carries out spray carbon processing.
Embodiment 3
Nickel foam is soaked into 5min in 30% concentrated nitric acid first, the oxide layer on surface is removed, then by 1.46g Co (NO3)26H2O, 0.37g NH4F and 1.5g CO (NH2)2It is dissolved in 50 milliliters of distilled water, whole adition process is stirred in magnetic force Mix lower progress.After stirring 30 minutes, in the autoclave that whole mixed solution is moved into inner liner polytetrafluoroethylene, it will cut Nickel foam be put into tetrafluoroethene, reaction solution loading 80%, at a certain temperature (120 DEG C) reaction 5h.After reaction, etc. Treat that it is cooled to room temperature scope, then three times are alternately cleaned with deionized water and ethanol to go the removal of impurity, then at 80 DEG C 12h is handled in drying box.High-temperature roasting 3h under the conditions of last 450 DEG C, obtains required product.Soluble silicon source is dissolved in ion In liquid system, by with the Co of the direct growth nickel foam of preparation3O4Nano-array is used as inertia sun as negative electrode, Pt nets electrode Pole, contains 0.25M SiCl at 50 DEG C4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage -2.6V, electrolysis time 2h, Electro-deposition product cleaning solution is organic solvent-acetone, and elemental silicon is obtained after washing.By the Co of above-mentioned preparation3O4- Si is placed on KYKY SBC-2 surface treating machines instrument carries out spray carbon processing.
The present invention is described in detail above, it is clear that as long as essentially without the inventive point and effect that depart from the present invention Really, will be readily apparent to persons skilled in the art deformation, also be all contained within protection scope of the present invention.

Claims (7)

1. a kind of three-dimensional compound Co3O4The preparation method of-Si-C negative materials, it is characterised in that comprise the following steps:
(1) it regard nickel foam as conductive current collector after low-kappa number;
(2) nickel foam after acid treatment is transferred in the reactor of the mixed aqueous solution equipped with cobalt nitrate, urea and ammonium fluoride, Heating response kettle, and constant temperature is for a period of time, is then cooled to room temperature, Co is made through high-temperature calcination after drying in product washing3O4Receive Nanowire structure array;
(3) soluble silicon source is dissolved in ion liquid system, so that product is negative electrode made from above-mentioned steps (2), with inertia Electric level 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) product prepared with above-mentioned steps (3) carries out spray C Surface processing.
2. method according to claim 1, it is characterised in that low-kappa number is 30% by nickel foam described in step (1) Concentrated nitric acid in soak 5min.
3. method according to claim 1, it is characterised in that mixed aqueous solution described in step (2) is by 1.0-3.0g nitre Sour cobalt, 0.3-0.5g ammonium fluorides and 1.0-3.0g urea are dissolved in 50mL distilled water, stir 30 minutes gained.
4. method according to claim 1, it is characterised in that reactor is inner liner polytetrafluoroethylene described in step (2) Autoclave.
5. method according to claim 1, it is characterised in that heating response kettle described in step (2) be carried out at 120 DEG C it is anti- 1-5h is answered, product is calcined 3h under the conditions of 350-450 DEG C.
6. method according to claim 1, it is characterised in that electro-deposition product is contained at 50 DEG C described in step (3) 0.25M SiCl4Quaternary ammonium salt ionic liquid in silicon electrolyzation obtain.
7. method according to claim 1, it is characterised in that it is to use KYKY that C Surface processing is sprayed described in step (4) SBC-2 surface treating machines carry out spray carbon processing, and C layers are coated in material surface.
CN201710031319.4A 2017-01-17 2017-01-17 A kind of compound Co of three-dimensional3O4The preparation method of-Si-C negative electrode material Expired - Fee Related CN107068993B (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN108615620A (en) * 2018-06-20 2018-10-02 华南理工大学 It is a kind of using nickel foam as the carbon nanotube of substrate/metal sulfide combination electrode and preparation method thereof
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
CN109524640A (en) * 2018-10-19 2019-03-26 西安科技大学 A kind of flexible self-supporting lithium ion battery negative material and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2010040985A1 (en) * 2008-10-10 2010-04-15 Nexeon Ltd A method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries
CN103098263A (en) * 2010-09-09 2013-05-08 加州理工学院 Electrochemical energy storage systems and methods
CN101970104B (en) * 2007-11-09 2013-11-06 华盛顿州立大学研究基金会 Catalysts and related methods
EP2533331B1 (en) * 2007-07-17 2015-08-19 Nexeon Limited Structured particles composed of silicon or a silicon-based material and method of fabricating thereof
CN105449173A (en) * 2014-08-29 2016-03-30 国家纳米科学中心 Cavity-structuralized silicon-carbon core-shell nanowire array, and preparation method and use thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2533331B1 (en) * 2007-07-17 2015-08-19 Nexeon Limited Structured particles composed of silicon or a silicon-based material and method of fabricating thereof
CN101970104B (en) * 2007-11-09 2013-11-06 华盛顿州立大学研究基金会 Catalysts and related methods
WO2010040985A1 (en) * 2008-10-10 2010-04-15 Nexeon Ltd A method of fabricating structured particles composed of silicon or a silicon-based material and their use in lithium rechargeable batteries
CN103098263A (en) * 2010-09-09 2013-05-08 加州理工学院 Electrochemical energy storage systems and methods
CN105449173A (en) * 2014-08-29 2016-03-30 国家纳米科学中心 Cavity-structuralized silicon-carbon core-shell nanowire array, and preparation method and use thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN108615620A (en) * 2018-06-20 2018-10-02 华南理工大学 It is a kind of using nickel foam as the carbon nanotube of substrate/metal sulfide combination electrode 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
CN109524640A (en) * 2018-10-19 2019-03-26 西安科技大学 A kind of flexible self-supporting lithium ion battery negative material and preparation method thereof
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

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