CN106207137A - A kind of composite negative electrode material of lithium ion battery and preparation method thereof - Google Patents
A kind of composite negative electrode material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN106207137A CN106207137A CN201610817095.5A CN201610817095A CN106207137A CN 106207137 A CN106207137 A CN 106207137A CN 201610817095 A CN201610817095 A CN 201610817095A CN 106207137 A CN106207137 A CN 106207137A
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—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
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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 a kind of composite negative electrode material of lithium ion battery and preparation method thereof, wherein, this composite includes charcoal clad and the kernel by this charcoal clad parcel, and wherein, described kernel is for including Fe3O4, the Fe of tri-kinds of compositions of FeO and Fe3O4/ FeO/Fe is combined kernel.The present invention is by improving the preparation technology that this composite is crucial, directly with micro-nano size α Fe2O3Granule makees presoma, does dispersant, reducing agent and charcoal source with organic compound or macromolecular compound, uses heat treatment method to prepare, is effectively simplified preparation technology, is highly suitable for producing in batches on a large scale；Further, when this composite uses as negative electrode, can effectively buffer the change in volume of charge/discharge process to structural damage, improve electrode material electric conductivity, improve specific capacity, cyclical stability and the high rate performance of this material charge/discharge process.
Description
Technical field
The invention belongs to technical field of chemical power, more particularly, to a kind of negative electrode for lithium ion battery composite
And preparation method thereof, this composite is specially Fe3O4/ FeO/Fe/C composite, is particularly suitable as negative material for lithium
Ion battery.
Background technology
Recent two decades comes, and owing to having the good characteristic such as high-energy-density and high output voltage, lithium ion battery is the most extensive
As portable electric appts energy source device.Although a large amount of novel energy-storing technology, such as lithium-sulfur cell, lithium-air battery and sodium ion
Batteries etc. are applied to propose challenge, but lithium ion battery is still electric automobile of future generation and plug-in hybrid-electric car moves
The prioritizing selection of power.People exploitation high-energy-density, high power density, the long life, high rate during charging-discharging new
Type electrode material aspect has paid great efforts, to meet ever-increasing performance requirement.Research finds, transition metal oxide
(MOx, M:Fe, Co, Ni etc.) compare current commercialization negative material (graphite) and have higher specific capacity (600～1000mAh/
G), it is the class lithium ion battery negative material with application prospect, has recently attracted the research interest that people are huge.This kind of
In material, magnetic iron ore (Fe3O4) owing to having high theoretical specific capacity (926mAh/g), low cost, close friend nontoxic, ecological, nature
The advantage of rich reserves, is a kind of negative material holding promise for most lithium ion battery.But, lithium ion embedding de-during huge
Big change in volume makes crystal grain be destroyed, and reduces the electrical contact between negative material and collector so that without adding
The Fe of work3O4Material circulation poor-performing, seriously hinders the commercial applications of this material.And, lasting active material particle
Rupture the SEI film that also can destroy surface of active material, make discharge and recharge reaction reversibility reduce, cause capacity to decay rapidly.
People have employed many methods to overcome these problems, wherein has two kinds of methods to be well used.One is synthesis
There is the nanometer Fe of various structure3O4Material, such as nano-particle, nanometer sheet, nano wire, nanotube and hollow nanostructures,
These structures can absorb lithium ion embedding de-during the mechanical tension that produces, shorten lithium ion transport path.But, these are received
Rice material in the overwhelming majority can not large-scale production, hinder actual application.And, nanorize can not solve electrode material relatively
The electric conductivity of difference.Another kind of method is by Fe3O4With Carbon Materials be combined, these Carbon Materials include graphite, carbon nanotube (CNT) with
And amorphous carbon.These Carbon Materials not only increase active material electron conduction, it is also possible to suppress granule as base material
Reunite, and buffer volumes can change the destruction that structure is caused, thus enhance composite cyclical stability.Amorphous carbon can
To be obtained by carbonization Organic substance, but at pre-synthesis electroactive material Surface coating amorphous carbon, it usually needs increase conjunction more
Become step, make preparation process more complicated.Therefore, in the urgent need to a kind of short-cut method of development in electroactive nanometer Fe3O4Material surface
Cladding amorphous carbon, makes composite have more conductive center.
Summary of the invention
For disadvantages described above or the Improvement requirement of prior art, it is an object of the invention to provide a kind of lithium ion battery and use
Composite negative pole material and preparation method thereof, wherein by improving the preparation technology that this composite is crucial, directly with receiving
Meter ruler cun α-Fe2O3Granule makees presoma, does dispersant, reducing agent and charcoal source with organic compound or macromolecular compound, uses
Prepared by heat treatment method, be effectively simplified preparation technology, is highly suitable for producing in batches on a large scale；Further, at organic compound
In thing or macromolecular compound carbonization process, amorphous carbon is tightly wrapped in ferric oxide particles outer layer and forms charcoal clad, simultaneously
Fe2O3It is reduced to Fe online3O4, FeO and Fe, so can form close intermolecular contacts between charcoal and ferric oxide particles；
Owing to the layer of charcoal of cladding is at each Fe3O4Connection is established, when this composite is as lithium ion between/FeO/Fe nano-particle
When battery cathode uses, it is possible not only to improve the electron conduction of material, it is also possible to the effectively volume of buffering charge/discharge process becomes
Change structural damage, improve specific capacity, cyclical stability and the high rate performance of this material charge/discharge process, be greatly improved
The chemical property of electrode material.
For achieving the above object, according to one aspect of the present invention, it is provided that a kind of lithium ion battery composite negative pole material
Material, it is characterised in that this composite includes charcoal clad and the kernel by this charcoal clad parcel, and wherein, described kernel is
Including Fe3O4, the Fe of tri-kinds of compositions of FeO and Fe3O4/ FeO/Fe is combined kernel.
It is another aspect of this invention to provide that the invention provides the preparation side of above-mentioned composite negative electrode material of lithium ion battery
Method, it is characterised in that comprise the following steps:
(1) by ball-milling method by α-Fe2O3Raw material and carbon source raw material are mixed to get the presoma of mix homogeneously；Described α-
Fe2O3The particle diameter of raw material is nanoscale or micron order, described carbon source raw material be in organic compound and macromolecular compound at least
A kind of；
(2) presoma obtained in described step (1) is carried out heat treatment in controlled atmosphere, make the institute in this presoma
State carbon source raw material carbonization and form charcoal clad, simultaneously Fe2O3It is reduced formation Fe3O4/ FeO/Fe composite nanometer particle, thus
Obtain composite negative electrode material of lithium ion battery eventually；
Described controlled atmosphere is at least one in noble gas, nitrogen and air；Described noble gas is preferably argon.
As present invention further optimization, in described step (2), described heat treatment is 600 DEG C～the temperature of 800 DEG C
Lower process 1h～10h.
As present invention further optimization, in described step (1), described carbon source raw material is saccharide, and polyacrylic acid is birdsed of the same feather flock together
Compound, polyacrylate polymers, at least one in the derivant that polyolefin polymers is corresponding with each of which.
As present invention further optimization, in described step (1), described α-Fe2O3Raw material and described carbon source raw material
Mass ratio be 1:0.2～1:10.
As present invention further optimization, before the described heat treatment in carrying out described step (2), described presoma
Also have passed through dried；Preferably, the baking temperature of this dried is 60 DEG C～120 DEG C.
By the above technical scheme that the present invention is contemplated, compared with prior art, due to directly with large-scale production
Micro-nano size α-Fe2O3Granule makees presoma, then does dispersant, reducing agent and charcoal with organic compound or macromolecular compound
Source, uses heat treatment method to prepare.In organic compound or macromolecular compound carbonization process, amorphous carbon tightly wraps
It is rolled in ferric oxide particles outer layer.Meanwhile, Fe2O3It is reduced to Fe online3O4, FeO and Fe, so can be in charcoal (corresponding charcoal cladding
Layer) and ferric oxide particles (i.e. Fe2O3It is partially reduced formed Fe3O4/ FeO/Fe nano-particle, namely Fe3O4/FeO/
Fe kernel) between form close intermolecular contacts.Cladding layer of charcoal establishes connection between particles, not only increases material
Electron conduction, has also buffered the change in volume of charge/discharge process to structural damage.Additionally, this complex exists a small amount of
Fe can be greatly enhanced electric conductivity.When as lithium ion battery negative material, Fe prepared by above method3O4/FeO/
Fe/C composite shows height ratio capacity, excellent cycling stability, the good remarkable storage lithium characteristic such as the most forthright, illustrates this
Material is used as the great potential of lithium ion battery high magnification negative material.
Composite negative electrode material of lithium ion battery (i.e. Fe in the present invention3O4/ FeO/Fe/C composite) it is charcoal cladding
Fe3O4/ FeO/Fe composite (i.e. includes Fe3O4/ FeO/Fe kernel and charcoal clad)；Accordingly, this lithium in the present invention
The preparation method of ion battery composite negative pole material, is the online solid phase synthesis process of kind of composite.
The present invention can overcome the defect that material conductivity in prior art is poor, synthetic method is complicated, it is provided that a kind of easy
The online solid phase synthesis process of tool operability, the ferric oxide nanometer particle of preparation cladding amorphous carbon.The amorphous carbon of synthesis
Tightly it is wrapped in ferric oxide particles outer layer, Fe2O3It is reduced to Fe online in situ3O4, FeO and Fe, between charcoal and ferric oxide particles
Formed and be in close contact.Cladding layer of charcoal sets up connection between granule, not only provides material conductivity, has also buffered charge/discharge process
Change in volume is to structural damage.Complex exists a small amount of Fe material conductivity also can be greatly improved.
Accompanying drawing explanation
Fig. 1 is the synthetic method schematic diagram of composite negative electrode material of lithium ion battery of the present invention；
Fig. 2 (a) is Fe3O4/ FeO/Fe/C composite XRD diffraction pattern, Fig. 2 (b) is Raman spectrogram, and Fig. 2 (c) is XPS figure
Composing complete collection of illustrative plates, Fig. 2 (d) is the fine collection of illustrative plates of XPS of Fe2p；
Fig. 3 (a) and Fig. 3 (b) is Fe3O4Field emission scanning electron microscope (FESEM) figure of/FeO/Fe/C composite,
Fig. 3 (c) is transmission electron microscope (TEM) figure, and Fig. 3 (d) is high resolution transmission electron microscope (HRTEM) figure；
Fig. 4 is Fe3O4The last fortnight charging and discharging curve of/FeO/Fe/C composite electrode；
Under the conditions of Fig. 5 is various multiplying power, Fe3O4/ FeO/Fe/C composite electrode charging and discharging capacity relative cycle cycle
Curve；
Fig. 6 is Fe3O4First all charging and discharging curves of/FeO/Fe/C composite electrode；
Fig. 7 is Fe3O4First all charging and discharging curves of/FeO/Fe/C composite electrode.
Detailed description of the invention
In order to make the purpose of the present invention, technical scheme and advantage clearer, below in conjunction with drawings and Examples, right
The present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, and
It is not used in the restriction present invention.If additionally, technical characteristic involved in each embodiment of invention described below
The conflict of not constituting each other just can be mutually combined.
Embodiment 1
This embodiment use ball-milling method uniformly mix 1g nanometer α-Fe2O3Presoma is prepared with 0.60g glucose.
Above-mentioned presoma is dried in 80 DEG C of stoves, the most under an argon atmosphere 650 DEG C of heat treatment 4h, makes glucose carbonization be formed
Amorphous carbon clad, meanwhile, Fe2O3Partial reduction forms Fe3O4/ FeO/Fe nano-particle.Finally give Fe3O4/FeO/Fe/
C composite.Building-up process is as shown in Figure 1.
Fe3O4The composition of/FeO/Fe/C composite and phase structure use xrd method to detect, as shown in Figure 2 a.The brightest
Aobvious, in XRD figure spectrum, all cognizable diffraction maximums can be at centroid structure magnetic iron ore (Fe3O4-JCDPS 19-0629), oxidation
The diffracting spectrum of ferrum (FeO-JCDPS 75-1550) and ferrum (Fe-JCDPS 87-0721) finds corresponding peak.Not observation
To the impurity diffraction maximum that other are other.Raman spectrum analysis observes the result of product as shown in Figure 2 b further, 1338cm-1D
Band and 1591cm-1G band confirm material exists amorphous carbon structure.
Fig. 2 c represents Fe3O4The complete XPS collection of illustrative plates of/FeO/Fe/C composite, shows in sample containing Fe, C and O element.
Fe 2p3/2 and Fe 2p,1/2 two characterizes the fine spectral peak of peak Fe 2p, lays respectively at 711eV and 725eV (see Fig. 2 d), it was demonstrated that
Material defines Fe3O4And FeO.～719eV does not observes Fe2O3Satellites, shows to there is not γ-Fe2O3, this XRD figure is composed
With Fe3O4Collection of illustrative plates is similar.
Prepared Fe3O4The pattern of/FeO/Fe/C composite and structure use field emission scanning electron microscope
(FESEM) detect with transmission electron microscope (TEM).Fig. 3 a and 3b represents prepared material is carried out panorama observation, aobvious
Shown a kind of by～the extreme close-packed structure that formed of 30nm diameter nano-particle.Can be clearly viewed in the TEM figure of Fig. 3 c
Being coated with amorphous carbon to nano grain surface, these charcoals are by the online carbonization of glucose in presoma.Charcoal nanometer is coated with
Not only make Fe in presoma2O3It is reduced into Fe online3O4, FeO and Fe, but also serve as in whole close-packed structure substrate and
Cementation.(see Fig. 3 d) in HRTEM figure, the boundary between charcoal and ferric oxide particles, lattice can be clearly observed
Border is orientated.Measuring the interplanar distance obtained is 0.253nm, 0.296nm and 0.203nm, corresponds respectively to Fe3O4Phase
(311), (220) crystal face, and (110) crystal face of Fe phase, further disclose Fe3O4, the existence of FeO and Fe.
Fig. 4 is 0.01V～3.0V potential window, electric current density 100mA/g, Fe3O4/ FeO/Fe/C composite electrode
The last fortnight charging and discharging curve, first all specific discharge capacities of material reach more than 1000mAh/g.
Under the conditions of Fig. 5 is various multiplying power, Fe3O4/ FeO/Fe/C composite electrode charging and discharging capacity relative cycle cycle
Curve, as seen from the figure, under 0.01～3.0V potential window, by Fe3O4/ FeO/Fe/C composite electrode is 0.1～10A/
G current density range carries out charge and discharge cycles.Even if under up to 10A/g electric current density, sample still can release about 400mAh/
G reversible specific capacity.When electric current density returns to initial 0.1A/g, it is original initial that sample remains to release close to 1200mAh/g
The specific capacity value of amount of capacity, it is shown that excellent high rate performance.
Embodiment 2
This embodiment use ball-milling method uniformly mix 1g nanometer α-Fe2O3Forerunner is prepared with 0.9g Kynoar
Body.Being dried in 80 DEG C of stoves by above-mentioned presoma, 700 DEG C of heat treatment 10h, make Kynoar the most in a nitrogen atmosphere
Carbonization forms amorphous carbon clad, meanwhile, Fe2O3Partial reduction forms Fe3O4/ FeO/Fe nano-particle.Finally give
Fe3O4/ FeO/Fe/C composite.Building-up process is as shown in Figure 1.
Fig. 6 is 0.01～3.0V potential window, electric current density 100mA/g, Fe3O4The head of/FeO/Fe/C composite electrode
All charging and discharging curves, the specific discharge capacity of material reaches nearly 1000mAh/g.
Embodiment 3
This embodiment use ball-milling method uniformly mix 1g nanometer α-Fe2O3Presoma is prepared with 2g Kynoar.
Being dried in 80 DEG C of baking ovens by above-mentioned presoma, installed in embedment carbon dust with crucible with cover by presoma, whole device exists
The lower 800 DEG C of heat treatment 1h of air atmosphere, make Kynoar carbonization form amorphous carbon clad, meanwhile, Fe2O3Partial reduction
Form Fe3O4/ FeO/Fe nano-particle.Finally give Fe3O4/ FeO/Fe/C composite.Building-up process is as shown in Figure 1.
Fig. 7 is 0.01～3.0V potential window, electric current density 100mA/g, Fe3O4The head of/FeO/Fe/C composite electrode
All charging and discharging curves, the specific discharge capacity of material reaches nearly 600mAh/g.
Fe in the present invention3O4It is nanoscale (i.e. Fe that/FeO/Fe is combined its size of kernel3O4/ FeO/Fe is compound to be received
Rice grain), α-Fe2O3The particle diameter of raw material is also that nanoscale is (due to this α-Fe2O3Raw material is by ball-milling treatment, mechanical milling process meeting
The particle diameter making raw material reduces further, therefore this α-Fe2O3The particle diameter of raw material can also be micron order, as long as ultimately generating
Fe3O4It is nanoscale that/FeO/Fe is combined the size controlling of kernel).
Carbon source in above-described embodiment, such as glucose, Kynoar, it is also possible to birds of the same feather flock together with other saccharides, polyacrylic acid
The derivant replacement that compound, polyacrylate polymers, polyolefin polymers and each of which are corresponding；Accordingly, at heat
The temperature-controllable of reason is made as 600 DEG C～800 DEG C, and the time of heat treatment is controllable to 1h～10h, so that it is guaranteed that the carbon of these carbon sources
Change.α-Fe2O3The ratio of raw material and carbon source raw material, also can be at 1:0.2～1:10 in addition to the concrete ratio in above-described embodiment
Distribution, to guarantee Fe3O4The thickness of the charcoal clad on/FeO/Fe composite nanometer particle surface.Polymer in the present invention can be
Homopolymer, copolymer.Ball-milling method blend step in the present invention, both can use dry ball milling, it would however also be possible to employ wet ball grinding,
Wet ball grinding can first add dehydrated alcohol and carry out ball milling again.
As it will be easily appreciated by one skilled in the art that and the foregoing is only presently preferred embodiments of the present invention, not in order to
Limit the present invention, all any amendment, equivalent and improvement etc. made within the spirit and principles in the present invention, all should comprise
Within protection scope of the present invention.
Claims (6)
1. a composite negative electrode material of lithium ion battery, it is characterised in that this composite includes charcoal clad and by this charcoal
The kernel of clad parcel, wherein, described kernel is for including Fe3O4, the Fe of tri-kinds of compositions of FeO and Fe3O4In/FeO/Fe is compound
Core.
2. the method preparing composite negative electrode material of lithium ion battery as claimed in claim 1, it is characterised in that include following step
Rapid:
(1) by ball-milling method by α-Fe2O3Raw material and carbon source raw material are mixed to get the presoma of mix homogeneously；Described α-Fe2O3Former
The particle diameter of material is nanoscale or micron order, and described carbon source raw material is at least one in organic compound and macromolecular compound；
(2) presoma obtained in described step (1) is carried out heat treatment in controlled atmosphere, make the described carbon in this presoma
Source raw material carbonization forms charcoal clad, simultaneously Fe2O3It is reduced formation Fe3O4/ FeO/Fe composite nanometer particle, thus final
To composite negative electrode material of lithium ion battery；
Described controlled atmosphere is at least one in noble gas, nitrogen and air；Described noble gas is preferably argon.
3. the preparation method of composite negative electrode material of lithium ion battery as claimed in claim 2, it is characterised in that described step
(2), in, described heat treatment is process 1h～10h at a temperature of 600 DEG C～800 DEG C.
4. the preparation method of composite negative electrode material of lithium ion battery as claimed in claim 2, it is characterised in that described step
(1), in, described carbon source raw material is saccharide, polyacrylic polymer, polyacrylate polymers, polyolefin polymers and
At least one in the derivant that each of which is corresponding.
5. the preparation method of composite negative electrode material of lithium ion battery as claimed in claim 2, it is characterised in that described step
(1) in, described α-Fe2O3Raw material is 1:0.2～1:10 with the mass ratio of described carbon source raw material.
6. the preparation method of composite negative electrode material of lithium ion battery as claimed in claim 2, it is characterised in that described in carrying out
Before described heat treatment in step (2), described presoma also have passed through dried；Preferably, this dried is dry
Temperature is 60 DEG C～120 DEG C.
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| CN109524633A (en) * | 2017-09-19 | 2019-03-26 | 丰田自动车株式会社 | The manufacturing method and aquo-lithium ion secondary cell and its manufacturing method of negative electrode active material complex |
| CN109524633B (en) * | 2017-09-19 | 2022-03-15 | 丰田自动车株式会社 | Method for producing negative electrode active material composite, aqueous lithium ion secondary battery, and method for producing same |
| CN108183213A (en) * | 2017-12-27 | 2018-06-19 | 肇庆市华师大光电产业研究院 | A kind of preparation method of di-iron trioxide/carbon/carbon nanotube lithium battery negative material |
| CN114538569A (en) * | 2022-02-25 | 2022-05-27 | 中国科学技术大学 | Fe coated with chitosan-derived carbon shell0/FeOxGranular electro-Fenton cathode and preparation and application thereof |
| CN114538569B (en) * | 2022-02-25 | 2023-03-10 | 中国科学技术大学 | Fe coated with chitosan-derived carbon shell 0 /FeO X Granular electro-Fenton cathode and preparation and application thereof |
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