CN108063240A - A kind of preparation method of zinc oxide/carbon composite available for negative electrode of lithium ion battery - Google Patents

A kind of preparation method of zinc oxide/carbon composite available for negative electrode of lithium ion battery Download PDF

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CN108063240A
CN108063240A CN201711449883.4A CN201711449883A CN108063240A CN 108063240 A CN108063240 A CN 108063240A CN 201711449883 A CN201711449883 A CN 201711449883A CN 108063240 A CN108063240 A CN 108063240A
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zinc oxide
coo
ion battery
pvp
lithium ion
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张永光
王新
钊妍
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Zhaoqing South China Normal University Optoelectronics Industry Research Institute
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Zhaoqing South China Normal University Optoelectronics Industry Research Institute
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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
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • 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 present invention is a kind of preparation method of zinc oxide/carbon composite available for negative electrode of lithium ion battery.This method comprises the following steps：(1) precursor liquid is prepared；(2) precursor liquid prepared is placed in needle tubing, Zn (CH is obtained with electrostatic spinning technique3COO)2/ PVP nano fibrous membranes；(3) pre-oxidized；(4) obtained substance will be pre-oxidized, is put into tube furnace, passes to argon gas, 1~2h is calcined at a temperature of 700~900 DEG C, finally obtains zinc oxide/carbon composite available for negative electrode of lithium ion battery.The present invention can be by regulating and controlling Zn (CH3COO)2Zinc oxide/carbon composite that obtain carbon content from the ratio of carbon source PVP different, zinc oxide mixed with carbon it is more uniform, it is easy to operate, and save cost.

Description

A kind of preparation of zinc oxide/carbon composite available for negative electrode of lithium ion battery Method
Technical field
The present invention relates to technical fields prepared by lithium ion battery negative material, are related to a kind of oxygen of negative electrode of lithium ion battery Change the preparation method of zinc/carbon composite.Nano zine oxide is the wide band gap semiconductor for having advantageous property, wherein Static Spinning For silk method as nanofiber most one of simple effective method is prepared, Electrospun nano-fibers have big surface area, high The advantages that porosity and unique structure nano characteristic, there is potential using value.
Background technology
With the development of electronics industry, lithium ion battery applications are increasingly extensive, and the requirement for stability is also higher and higher. Current 21st century, lithium ion battery further solve energy crisis as emerging energy storage device and realize the hope of environmental protection. Electrolyte is different according to used in lithium battery, is divided into two major class of liquid lithium battery and poly-lithium battery, the main distinction exists It is different in electrolyte.Lithium ion battery is the innovative product of lithium battery, but lithium is a kind of metal of high activity, when charging It is present with the situation of burning and explosion, the active ingredient of elemental lithium can be inhibited by being added in new type lithium ion battery, such as nickel, manganese Deng having reached safe efficient, convenient plasticity.The polymer Li-ion battery of a new generation is in the degree of polymerization On it is very high, obtain thin type, the flexibility for improving battery moulding in shape, coordinate product demand, make any capacity Battery.Polymer Li-ion battery is divided into three classes：(1) solid polymer electrolyte lithium ion battery (2) gelatin polymer electricity Solve the lithium ion battery of matter lithium ion battery (3) polymers as cathode materials.
This patent prepares a kind of system of the ZnO/ carbon composites for negative electrode of lithium ion battery using electrostatic spinning technique Standby, same domain patent CN105591090A reports a kind of zinc oxide/nitrogen carbon dope composite material available for negative electrode of lithium ion battery Preparation method, be it is a kind of prepare nitrogen-doped carbon material using sol-gal process, but above-mentioned patent has the following disadvantages：1 body Product easily 2 preparation processes of expansion are complicated.
Therefore, simplify preparing lithium ion battery zinc negative material technique, high efficiency and high-environmental and can safeguard Charged storage capacity is the key that improve such battery performance.
Method of electrostatic spinning is that polymer solution or melt carry out injection stretching under electrostatic interaction and obtain nano-scale fiber Spinning process, early in the 1930s, reported in the patent utilize high-voltage electrostatic field carry out spinning, electrostatic spinning dress It puts and is mainly made of high voltage power supply, solution storage device and injection apparatus and four parts of reception device, storage device uses Syringe and No. 22 injector heads fill storing liquid, and are inserted into metal electrode.The electrode is connected with high voltage power supply, makes liquid charged. Using being placed in parallel, slowly syringe is promoted to come out Solution extrusion using mobile phone mechanical device of controlling interest.Reception device is roller. It is reported that spacing between fiber is 1-2 microns, the reason for spacing is generated between fiber is to generate repulsive interaction in fiber, from And make have certain spacing between fiber and fiber.Spacing size is related with size and residual charge amount.Though electrostatic spinning technique It is so rapidly developed by its advantage, but it is due to the limitation of its own, how to be combined with related substances practical, also permitted More problems need to solve.
Zinc oxide/carbon composite can improve the surface that metal ion load is distributed to carbon material, also improve electrification Property is learned, with the good storage lithium of carbon recombination energy while improving Volumetric expansion, the specific capacity of composite material can be increased.
This patent is to prepare zinc oxide carbon dope using method of electrostatic spinning.Its electrostatic spinning principle：By polymer solution or Melt is placed in liquid storage pipe, and liquid storage pipe is placed in electric field, and anode is inserted into the solution of liquid storage pipe, and anode is sent out from high-voltage electrostatic field Raw device export.When there is no applied voltage, due to the solution in memotron it is affected by gravity and slowly along liquid storage tube wall stream It drops down, and the adhesion strength and solution between solution and liquid storage tube wall be in itself under the comprehensive function of possessed viscosity and surface tension, Form the drop for being suspended on liquid storage nozzle.
When power plant opens, due to electric field action, the part with polarity will be to the moon in different lewis' acids in solution Extreme direction is assembled.Since anode is inserted into polymer solution, the surface of solution should be covered with the sun for being subject to anode repulsive interaction Short of electricity subdivision in lewis' acid, so the molecule of solution surface receives the electric field force that cathode is directed toward in direction, and solution The direction of electric field force that is subject to solution surface molecule of surface tension on the contrary, the electric field force produced by additional voltage is smaller When, electric field force is insufficient to allow electrically charged part in solution to be sprayed from solution, and at this moment liquid storage nozzle was that spherical drop is drawn originally It stretches elongated.Continue to increase applied voltage, it is when the voltage exceeds some critical value, molten in the case where extraneous other conditions are certain Electrically charged part overcomes the surface tension of solution to be sprayed from solution in liquid, and at this moment the drop of liquid storage nozzle becomes taper, is storing up Liquid pipe top forms one charged injection stream.Injection stream divides, and holds and volatilizees, fiber solidifying, and is arranged with unordered shape In the tunica fibrosa on collection device, forming similar non-woven cloth.
This method and traditional method are significantly different, in conventional spinning process, fiber under tension, and rheological force, gravity, Inertia force and aerodynamic effect.High polymeric solution or melt are then driven be subject to electric field force in electrostatic spinning, draw Stretch comes from the interaction between the charge in applied field and polymer jet flow, and has to polymer solution or melt After the high-pressure electrostatic for applying thousands of to up to ten thousand volts, polymer can just overcome surface tension to form injection thread, while spray Cure in journey with evaporation of the solvent, ultimately form nanofiber, diameter is generally between tens nanometers to several microns.For carbon materials For the preparation of material, it is longer to prepare nano zine oxide/graphene synthesis cycle with oxide-reduction methods such as Hummers, and material Pattern control it is more difficult uniformly.It is higher that zinc oxide/graphene cost is prepared using CVD method, and transfer process is with loss.
There is the formation state that several factors influence fiber during polymer electrospun, these factors include：(1) it is molten Fluidity matter, such as viscosity, electrical conductivity, surface tension, viscoplasticity etc. (2) technological parameter, if the quiet night of liquid storage pipe presses, current potential and liquid storage The distance between pipe and receiving screen etc..(3) environmental parameter, such as temperature, humidity and air velocity etc..
The property of solution influences the electrostatic spinning of polymer, and the dielectric constant of solvent is bigger, and the diameter of fiber is thinner.Air Humidity influence spinning fibre configuration of surface.
It is applied to filtering barrier material using electrostatic spinning technique.Nanofiber prepared by electrostatic spinning has greatly ratio Surface area and surface area ratio, while in the porous structure of fiber surface, make it have very strong adsorption capacity and good filtering Property, barrier property, adhesiveness and heat insulating ability.Sorbing material and filtering material can be made with it using these characteristics, applied to Asia Filtering of microparticles etc., when doing barrier material using the barrier property of nano material, due to stopping particle and certain ion Migration, as the membrane between micro battery positive and negative anodes.
The content of the invention
The mesh of the present invention is for deficiency present in current techniques, provides a kind of available for negative electrode of lithium ion battery material The preparation method of zinc oxide/carbon composite of material.This method obtains uniformly mixed Zn by electrostatic spinning technique (CH3COO)2The pattern of the zinc oxide/carbon composite obtained after its calcination is zinc oxide nano mitron by/PVP nano fibrous membranes Three-dimensional netted stereochemical structure is mutually staggered to form with chain carbon phase.Zinc oxide/carbon composite that the present invention obtains can be by changing It is apt to the material rate in electrostatic spinning process to regulate and control the content of the zinc oxide finally obtained and carbon, so as to solve zinc oxide conduct The defects of electric conductivity existing for lithium ion battery negative material is poor, volume change is big, manufacturing cost is high, long preparation period, from And the chemical property and cyclical stability of lithium ion battery are improved on the whole.
The technical scheme is that：
A kind of preparation method of zinc oxide/carbon composite available for negative electrode of lithium ion battery, comprises the following steps：
(1) precursor liquid is prepared：By Zn (CH3COO)2It is added in methanol, when magnetic agitation 1~5 is small, adds polyethylene Pyrrolidones-K9 (PVP) when continuation magnetic agitation 2~10 is small, obtains precursor liquid；Wherein, every 5~20ml methanol add 0.2~ 0.7gZn(CH3COO)2, 0.5~1.0g polyvinylpyrrolidones-K9 (PVP)；
(2) electrostatic spinning prepares Zn (CH3COO)2/ PVP nano fibrous membranes：The precursor liquid that 1~10mL is prepared is taken to be placed in pin Guan Zhong, using fltting speed as 0.15~0.2mm/min, syringe pump spinning 0.001~0.05ml/min of flow velocity, negative voltage for 1~ 2kv, positive voltage are 10~15kv, receive distance and carry out spinning, receiver board SiO for 15~25cm2/ Si is the aluminium foil of substrate, It is placed in again in vacuum drying chamber, 25 DEG C of dry 10~12h obtain Zn (CH3COO)2/ PVP nano fibrous membranes；
(3) Muffle furnace pre-oxidizes：Zn (the CH that upper step is obtained3COO)2It is dry after/PVP nanofiber Membrane cleanings, it places into Muffle furnace is warming up to 200~300 DEG C with the heating rate of 1~20 DEG C/min, keeps the temperature drying after 1~5h；
(4) obtained substance will be pre-oxidized, is put into tube furnace, passes to argon gas, with the heating rate liter of 1~10 DEG C/min Temperature finally obtains the zinc oxide available for negative electrode of lithium ion battery/carbon composite wood to 1~2h is calcined at a temperature of 700~900 DEG C Material.
Compared with prior art, beneficial effects of the present invention are as follows：
1st, the present invention by electrostatic spinning technique by Zn (CH3COO)2It is mixed with carbon source PVP, and passes through Muffle furnace calcination one Step reaction obtains the composite material of zinc oxide/carbon, and the addition of carbon adds the detection active site and electric conductivity of electrode, promotes The electron transmission on ZnO surfaces increases its effective adsorption site, and its operating process is simple, and fabrication cycle is short.
2nd, the present invention can be by regulating and controlling Zn (CH3COO)2The oxidation that obtain carbon content from the ratio of carbon source PVP different Zinc/carbon composite, zinc oxide mixed with carbon it is more uniform, it is easy to operate, and save cost.
3rd, before carbonization to Zn (CH3COO)2/ PVP nano fibrous membranes are pre-oxidized, and organic carbochain is made to preliminarily form annular Structure makes it be unlikely to crack in follow-up carbonisation.
4th, the present invention obtains uniformly mixed Zn (CH by electrostatic spinning technique3COO)2/ PVP nano fibrous membranes, are burnt The pattern of the zinc oxide/carbon composite obtained after burning is zinc oxide nano mitron and the interlaced three-dimensional netted solid of formation of carbochain Structure since zinc-oxide nano pipe diameter is 300~500nm, has huge specific surface area, can be by chain carbon adsorption at it Be formed about distribution and its uniform three-dimensional netted zinc oxide/carbon composite, this shorten charge and discharge process intermediate ion and The transmission path of electronics, so as to improve the electric conductivity of zinc oxide/carbon composite, also, zinc oxide nano mitron table on the whole Face has more pore space structure, and the net structure that this pore space structure and zinc oxide, carbochain are interlocked can be to charge and discharge process The volume change of middle zinc oxide provides larger space and comes into row buffering, so as to restrained effectively the crushing of electrode.
Description of the drawings
Fig. 1 is the X-ray diffractogram of zinc oxide/carbon composite prepared by embodiment 1.
Fig. 2 is the scanning electron microscope diagram of zinc oxide/carbon composite prepared by embodiment 1；
Fig. 3 is First charge-discharge curve under 0.1C.
Specific embodiment
Embodiment 1
The first step prepares zinc oxide/carbon composite for negative electrode of lithium ion battery：
1st, precursor liquid is prepared：Weigh the Zn (CH of 0.5054g3COO)2Be dissolved in 10ml methanol, and stir 2 it is small when, then To the Zn (CH stirred evenly3COO)20.8480g polyvinylpyrrolidones-K9 (PVP) is added in solution, is stood after stirring 5.5h.
2nd, electrostatic spinning prepares Zn (CH3COO)2/ PVP nano fibrous membranes：The precursor liquid that 3mL is prepared is taken to be placed in range be In the needle tubing of 5mL, using fltting speed as 0.18mm/min, syringe pump spinning flow velocity 0.01ml/min, negative voltage 1kv, positive electricity It presses as 12kv, receives distance and carry out the spinning (model of electrostatic spinning machine for 20cm：ET-1), receiver board SiO2/ Si is substrate Aluminium foil, make Zn (CHC3OO)2/ PVP nano fibrous membranes, place it in vacuum drying chamber, 25 DEG C of dry 12h.(after spinning The obtained actual compounding substances for polyvinylpyrrolidone (PVP) and zinc acetate of substance, threadiness can be formed by spinning Structure, through overload inert atmosphere under high-temperature calcination PVP be carbonized, zinc acetate becomes zinc oxide.)
3rd, Muffle furnace pre-oxidizes：By the Zn (CH of step 23COO)2/ PVP nano fibrous membranes are washed with deionized water from aluminium foil It crosses, is torn, be put into porcelain boat with tweezers after dry, with 2 DEG C/min of heating rate Muffle furnace is made to be warming up to 270 DEG C, heat preservation 2 is small When, be down to room temperature naturally, be put into vacuum drying chamber dry 12 it is small when.
4th, obtained substance will be pre-oxidized, is put into tube furnace, passes to argon gas, be warming up to the heating rate of 2 DEG C/min And 1h is calcined at this temperature, obtain zinc oxide/carbon composite by 800 DEG C.
Second step, the preparation of battery anode slice and the assembling of battery
Zinc oxide/carbon composite and conductive agent and binding agent grind according to the ratio that mass ratio is 8: 1: 1, are mixed into slurry Material, slurry is uniformly scratched on carbon containing aluminium foil, is dried at 60 DEG C for 24 hours, is pushed flakiness in 5MPa pressure using tablet press machine, is obtained It is anode using gained zinc oxide/carbon as cathode, metal lithium sheet to positive plate, lithium hexafluorophosphate electrolyte solution is added in, in glove box Battery assembling is carried out, obtains button CR2032 half-cells.
This step and tube furnace carbonization on other documents, which prepare tunica fibrosa and carry out comparison, to take advantage：It is aoxidized, pre- After oxidation, heating rate is used to continue heating carbonization for 2 DEG C/min, at the same time, Temperature fall takes out after 1 hour that is carbonized, Be finally putting into vacuum drying chamber 12 it is small when more than it is spare.Obtain the laboratory sample that calcining is complete and is come into full contact with air.
Method of electrostatic spinning can control aperture, the porosity of electrospinning fibre, system by adjusting the ingredient of spinning precursor liquid It is standby go out product homogeneity is good, easy film forming, ZnO nanotube/has the specific surface area of bigger and higher compared to ZnO nano fiber Porosity, and since nano-ZnO electric conductivity is poor, its application in terms of chemistry is limited, thus will have and well lead The carbon of electrical property and its compound expansible electrochemical applications scope of ZnO nanotube/.
ZnO is a kind of new wide bandgap compound semiconductor material, has unique optics and electrology characteristic.ZnO has There are the property more excellent than common zinc oxide material, such as fluorescence, piezoelectric material, varistor, magnetic material.In many materials In material, the flat film of the hexagonal lattice for the bi-dimensional cellular shape that graphene is made of carbon atom with the monoatomic layer that hydridization connects, It is widely used when there is high electric conductivity, high specific surface area and good chemical stabilization.The nanometer of zinc oxide There is recycling capacity attenuation and think very much the characteristics of rapid in zinc oxide, and zinc oxide carbon dope can just supply its defect.
Fig. 1 is the X-ray diffractogram of zinc oxide/carbon composite obtained by example 1.As can be seen that its all peak It is corresponding with zinc oxide, illustrate prepared by the present invention be high-purity zinc oxide, carbon peak unobvious be by zinc oxide institute it is right The peak intensity answered is high and sharp, this illustrates that the zinc oxide crystallinity obtained by the present invention is high, but is shown in the scanning electron of Fig. 2 The carbon of apparent chain structure can be observed in micro mirror figure.
Fig. 2 is the scanning electron microscope diagram of the doped zinc oxide carbon material obtained by example 1.There it can be seen that this hair Bright prepared zinc oxide/carbon composite has netted multi-joint 3-D solid structure, this is for zinc oxide as lithium ion Cell negative electrode material generated volume change in charge and discharge process can play apparent cushioning effect, the institute of the present invention made The lithium ion battery negative material of preparation has excellent cycle performance.
Fig. 3 is charge discharge curve of the zinc oxide carbon dope as lithium ion battery negative material obtained by example 1, It may be seen that under 0.1C current densities, the discharge capacity for the first time of the material is up to 826mAh/g, and coulombic efficiency is up to 96%, present good chemical property.
Embodiment 2
Other set 10 DEG C/min to 270 DEG C of Muffle furnace heating rate, constant temperature 2 with embodiment 1, difference for the 3rd step Hour, naturally near room temperature, be put into vacuum drying chamber dry 12 it is small when.
Embodiment 3
Other set 20 DEG C/min to 270 DEG C of Muffle furnace heating rate, constant temperature 2 with embodiment 1, difference for the 3rd step Hour, naturally near room temperature, be put into vacuum drying chamber dry 12 it is small when.
This patent it is simple for process efficiently, material high rate performance is greatly improved.Cathode is improved to a certain extent The comprehensive performance of zinc oxide carbon dope, nanofiber improve electric conductivity due to stable structure.
Unaccomplished matter of the present invention is known technology.

Claims (1)

1. a kind of preparation method of zinc oxide/carbon composite available for negative electrode of lithium ion battery, it is characterized in that this method bag Include following steps：
（1）Prepare precursor liquid：By Zn (CH3COO)2It is added in methanol, when magnetic agitation 1 ~ 5 is small, adds polyvinylpyrrolidine Ketone-K9（PVP）, when continuation magnetic agitation 2 ~ 10 is small, obtain precursor liquid；Wherein, every 5 ~ 20ml methanol adds 0.2 ~ 0.7gZn (CH3COO)2, 0.5 ~ 1.0g polyvinylpyrrolidones-K9（PVP）；
（2）Electrostatic spinning prepares Zn (CH3COO)2/ PVP nano fibrous membranes：The precursor liquid that 1 ~ 10mL is prepared is taken to be placed in needle tubing, Using fltting speed as 0.15 ~ 0.2mm/min, syringe pump spinning 0.001 ~ 0.05ml/min of flow velocity, negative voltage be 1 ~ 2kv, positive electricity It presses as 10 ~ 15kv, receives distance and carry out spinning, receiver board SiO for 15 ~ 25cm2/ Si is the aluminium foil of substrate, then is placed in vacuum In drying box, 25 DEG C of dry 10 ~ 12h obtain Zn (CH3COO)2/ PVP nano fibrous membranes；
（3）Muffle furnace pre-oxidizes：Zn (the CH that upper step is obtained3COO)2It is dry after/PVP nanofiber Membrane cleanings, place into Muffle Stove is warming up to 200 ~ 300 DEG C with the heating rate of 1 ~ 20 DEG C/min, keeps the temperature drying after 1 ~ 5h；
（4）Obtained substance will be pre-oxidized, be put into tube furnace, pass to argon gas, be warming up to the heating rate of 1 ~ 10 DEG C/min 1 ~ 2h is calcined at a temperature of 700 ~ 900 DEG C, finally obtains zinc oxide/carbon composite available for negative electrode of lithium ion battery.
CN201711449883.4A 2017-12-27 2017-12-27 A kind of preparation method of zinc oxide/carbon composite available for negative electrode of lithium ion battery Pending CN108063240A (en)

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CN109346690A (en) * 2018-09-30 2019-02-15 肇庆市华师大光电产业研究院 A kind of preparation method and application of nitrogen-doped carbon nano-fiber composite zinc oxide lithium ion battery negative material
CN109873147A (en) * 2019-03-04 2019-06-11 湘潭大学 A kind of carbon modification porous ZnO nano material and its preparation method and application
CN111554905A (en) * 2020-05-14 2020-08-18 云南民族大学 Preparation method, product and application of zinc oxide-based carbon composite nano material

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Publication number Priority date Publication date Assignee Title
CN109216704A (en) * 2018-09-12 2019-01-15 肇庆市华师大光电产业研究院 A kind of preparation method applied to the modified interlayer of anode in lithium-sulfur cell
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CN109346690A (en) * 2018-09-30 2019-02-15 肇庆市华师大光电产业研究院 A kind of preparation method and application of nitrogen-doped carbon nano-fiber composite zinc oxide lithium ion battery negative material
CN109873147A (en) * 2019-03-04 2019-06-11 湘潭大学 A kind of carbon modification porous ZnO nano material and its preparation method and application
CN109873147B (en) * 2019-03-04 2021-08-24 湘潭大学 Carbon-modified porous ZnO nano material and preparation method and application thereof
CN111554905A (en) * 2020-05-14 2020-08-18 云南民族大学 Preparation method, product and application of zinc oxide-based carbon composite nano material
CN111554905B (en) * 2020-05-14 2020-12-29 云南民族大学 Preparation method, product and application of zinc oxide-based carbon composite nano material

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