CN108178157A - A kind of sodium-ion battery negative material and its application and preparation method - Google Patents
A kind of sodium-ion battery negative material and its application and preparation method Download PDFInfo
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- CN108178157A CN108178157A CN201711332071.1A CN201711332071A CN108178157A CN 108178157 A CN108178157 A CN 108178157A CN 201711332071 A CN201711332071 A CN 201711332071A CN 108178157 A CN108178157 A CN 108178157A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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 present invention relates to chemical cell field, especially a kind of active material Ti of embedded type storage sodium mechanism3C2As sodium-ion battery negative material and its application and preparation method；The electrode material includes the Ti of the two-dimensional slice structure with sodium ion insertion ability3C2；It is of the invention that difference lies in apply a kind of nontoxic two-dimensional slice structural material Ti of novel environment friendly with other sodium ion negative materials3C2As electroactive material, insertion-host electrode materials have special lamellar structure, and the reversible insertion of sodium ion energy emerges in interlayer and do not destroy its structure, therefore with long circulation life and good high rate performance.
Description
Technical field
The present invention relates to chemical cell field, especially a kind of active material Ti of embedded type storage sodium mechanism3C2As sodium
Ion battery negative material and its application and preparation method.
Background technology
Energy storage technology is all kinds of energy application demands of balance, promotes the effective means of social integral energy service efficiency,
Extensive and distribution type renewable energy utilization, the exploration of urban distribution network peak load shifting, portable electronic product, the outer space etc. should
One of all have wide practical use with field, while be also the critical support technology of intelligent grid construction.In all kinds of energy storage skills
In art, the carrier of electrochemical energy storage is battery, in existing energy-storage battery system, lithium ion battery with its material system flexibly,
Technology innovation becomes energy-storage battery system of greatest concern, the extensive use in all kinds of demonstration projects soon.But current lithium
Ion battery safety problem not yet solves at all, and battery cost is higher, and with scale energy storage and electric vehicle engineering
It promotes and applies, lithium ion battery will be likely to be encountered the bottleneck of lithium resource shortage in future.As the metal member of the same clan with elemental lithium
Every physicochemical properties of element, sodium and lithium are closer to, and are contained abundant (elements of earth's crust reserves the 4th) in nature, storage
Amount has inborn cost advantage far above the lithium resource in South America is focused primarily upon, and be easy to purify.It is meanwhile most of existing
Sodium-ion battery material system operating voltage range it is consistent with water burning voltage window, use can be matched with water phase electrolyte,
With inborn security advantages.
At the end of the 20th century at the beginning of 21 century, world's main economic body has launched respectively battery technology development plan, in all kinds of rule
Sodium-ion battery is all classified as medium-long term target, but the actually reaction mechanism and material crystal structure of sodium-ion battery in drawing
Similar to lithium ion battery, material system matching principle and tackling problems in key technologies route can also use for reference lithium ion battery and show
Some experiences, so, technological break-through and product maturation time may be shorter than expected.At present, in the world some battery technologies compared with
Sodium-ion battery technology an important basic and perspective study field is classified as, and as not for advanced country
Come the energy storage electrochemical techniques developing direction paid close attention to.Wherein, the U.S. and Japan set up special support sodium ion electricity in the recent period
Pilot study early period of pool technology, China starts late in this respect, it is necessary to step up into line trace and the relevant technologies deposit.
Although sodium-ion battery obtains the favor of domestic and foreign scholars in recent years, the energy storage system new as one, sodium-ion battery
The key of development is the research of novel high-performance positive and negative pole material and electrolyte, the Research foundation based on lithium ion battery and
Commercialized development course, anode material of lithium-ion battery research relatively lag behind, and the reality for seriously constraining sodium-ion battery should
With.Studying more negative material at present mainly has：Carbon-based material, metal oxide, alloy etc..
Due to successful application of the graphite cathode in lithium ion battery, people generally have an optimistic view of carbon-based material in sodium ion electricity
Utilization in pond.Research shows that graphite cathode can not meet the needs of embedding sodium, thus capacity due to the limitation of interlamellar spacing
It is extremely low.It is that the carbon materials of various non-graphite structures shows the reversible deintercalation performance of good sodium ion, wherein hard carbon material instead
Performance is most prominent.Hard carbon material has macroscopical non-graphite structure, while includes graphite interlayer again in microstructure, such as：Resin
Carbon, carbon black etc..The hard carbon material of Komaba seminars report is in 25mAg-1There is down 240mAhg-1Embedding capacity, 100 times
200mAhg is maintained at after cycle-1, there is preferable cycle performance.Hard carbon material presently, there are the problem of be first circle coulombic efficiency
It is low, high rate performance is poor, cycle life is short.Mainly with metallic sodium reversible redox reaction occurs for transition metal oxide, so far
Until the present, the transition metal oxide for sodium-ion battery motor material is also fewer, and negative material mainly has：TiO2、α-
MoO3Deng.The problem of being primarily present includes that reversible capacity is smaller, cyclical stability is poor.Alloy type material is higher due to having
Theoretical specific capacity is increasingly becoming research hotspot, and sodium can form intermetallic compound at room temperature with various metals, and research has shown that Na
Alloy Na can be respectively formed with Sn, Sb, Ge, Pb etc.15Sn4、Na3Sb、Na3Ge and Na15Pb4, it is corresponding theoretical by calculating
Specific capacity is 845,660,1108 and 485mAhg respectively-1, but alloy type material generally existing during reversible deintercalation sodium
Irreversible volume expansion, leads to that capacity attenuation is fast, cyclical stability is poor, cycle life is short.At the research of sodium-ion battery
In the starting stage, the above material is also faced with much challenging before practical application.It is really suited for commercialized sodium ion
Cell negative electrode material needs to meet requirement as described below：Inexpensive, safe and non-toxic, good chemical property.
Embedded type anode material of lithium-ion battery is considered great development prospect, and insertion-host electrode materials generally have spy
Different lamellar structure, sodium ion can reversible insertion emerge in interlayer and do not destroy its structure, therefore with long circulation life and good
Good high rate performance.
Recently, Gogotsi etc. reports a series of special compounds, they have two-dimensional slice structure and have good
Good electric conductivity is named as MXenes according to element composition.The series compound is to pass through " A " layer atom in MAX phases
The method of wet-chemical removes and obtains the MXenes of two-dimensional slice structure, can use Mn+1AXnIt represents, wherein M represents transition gold
Belong to, A typically represents third and fourth major element, such as：Al, Ga, Si or Ge；X is C or N.MXenes series compounds are logical
It crosses and immerses the MAX powder containing Al in dense HF solution, it is former to etch away Al therein at a temperature of in room temperature or slightly heating
Son, such as： Ti3C2, Ti2C, Ti4C3, TiNbC and (V0.5Cr0.5)3C2Deng.The method of HF etchings makes MXenes adsorptions a large amount of
O, OH and the functional group containing F, this MXene containing surface functional group usually use Mn+1XnTXIt represents, wherein T represents surface official
It can roll into a ball, x represents the quantity of end group.
In recent years, using Gogotsi seminars as representative, domestic and international researcher is to MXenes series compounds from reason
Systematic research has been carried out by calculating to practical application：1st, the interlayer of two-dimensional slice structure MXenes can be embedded in organic macromolecule
Compound, such as：Hydrazine, DMSO and urea molecule；2nd, two-dimensional slice structure MXenes also has reversible embedding lithium characteristic, can conduct
Lithium ion battery negative material when being prepared into additive-free self-supporting electrode, has 410mAhg under 1C-1Electric discharge hold
Amount.3rd, it is a variety of cation in aqueous solution can spontaneous reversible insertion, abjection MXene interlayers, such as：Li+, Na+, Mg2+, K+, NH4 +
And Al3+, there is good chemical property in aqueous electrolyte system.4th, pass through first principle density functional theory meter
Calculating proves：Na+、K+、Ca2+MXenes interlayers can be embedded in, with Ti3C2For, the theoretical specific capacity of Na, K, Ca are respectively
351.8、191.8、319.8mAhg-1, compared with existing lithium/anode material of lithium-ion battery, MXenes has good answer
Use prospect.
It is demonstrated experimentally that Ti3C2Good chemical property is shown as lithium ion battery negative material；It is counted by theory
It calculates, Ti3C2It can realize the reversible embedding de- of sodium ion.But Na+Ionic radius be much larger than Li+, to realize that sodium ion is reversible
It is embedding de-, higher requirement will be proposed to two-dimensional layer material.Document report, increase graphene sheet layer interlamellar spacing can make its tool
There is embedding sodium activity.Similarly, increase Ti3C2Lamella interlamellar spacing is conducive to the reversible embedding de- of sodium ion, and still, increased interlamellar spacing will
Cause the Van der Waals force between lamella fainter, interlayer electric conductivity is made to be deteriorated.
Invention content
The purpose of the present invention is：Overcome deficiency of the prior art, provide and a kind of followed with high-energy density, length
The sodium-ion battery negative material in ring service life；Another object of the present invention is：Sodium-ion battery negative material is provided
Preparation method；A further object of the invention is：The application of sodium-ion battery negative material is provided.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows：
A kind of sodium-ion battery negative material, the electrode material include the two-dimensional slice with sodium ion insertion ability
The Ti of layer structure3C2。
Preferably, the Ti3C2It is made of less than 10 layers or more 50 layers lamellar structures.
Preferably, the Ti3C2Interlamellar spacing and lamella part lift-off processing are enlarged using DMSO or DMF.
Preferably, the multilayer two-dimension lamellar structure Ti3C2The processing that interlamellar spacing is enlarged using DMSO is specific as follows：
(1)Ti3AlC2Precise 1g is poured into plastic bottle with cover, and graduated cylinder measures the dense HF of 10mL and is poured slowly into plastics
Bottle, covers bottle cap and 18h is stirred at room temperature, and centrifuges, and gained precipitation is washed with distilled water, 80 DEG C of dryings of vacuum drying chamber
12h, it is spare；
(2) by the Ti obtained by back3C218h is stirred at room temperature with DMSO, centrifuges, by precipitation absolute ethyl alcohol and steaming
Distilled water is repeatedly washed, the dry 12h of 80 DEG C of vacuum drying chamber.
Preferably, the electro-chemical activity test point position section of the sodium-ion battery is 0-3V.
Preferably, the electrode material is used as the cathode of battery.
A kind of sodium-ion battery is assembled into the application of sodium ion half-cell with negative material under organic electrolyte system.
A kind of preparation method of sodium ion half-cell, the described method comprises the following steps：With the Ti of two-dimensional slice structure3C2
For electroactive material, mixed with conductive agent acetylene black, binding agent Kynoar, using N- methyl -2- pyrrolidones as solvent,
It is coated on copper foil of affluxion body after stirring evenly, then dry 12h is spare in 110 DEG C of vacuum drying chamber.
Preferably, the Ti of the two-dimensional slice structure3C2With conductive agent acetylene black, the mass ratio of binding agent Kynoar
8:1:1。
The advantageous effect of technical solution using the present invention is：
It is of the invention that difference lies in apply a kind of nontoxic two-dimensional slice of novel environment friendly with other sodium ion negative materials
Layer structural material Ti3C2As electroactive material, insertion-host electrode materials have special lamellar structure, and sodium ion can be reversible embedding
Enter to emerge in interlayer and do not destroy its structure, therefore with long circulation life and good high rate performance.
Description of the drawings
The present invention is further described with reference to the accompanying drawings and examples.
Fig. 1 is the Ti that embodiment 1,2 obtains3C2With with the processed Ti of DMSO3C2Scanning electron microscope (SEM) photograph；
Fig. 2 is the Ti that embodiment 1 obtains3C2XRD spectrum；
Fig. 3 a, b, c are the Ti of multilayer two-dimension lamellar structure3C2Make the first circle charge and discharge for the half-cell that sodium-ion battery cathode is assembled
Electricity, cycle life and high rate performance figure.
Specific embodiment
In conjunction with the accompanying drawings, the present invention is further explained in detail.These attached drawings are simplified schematic diagram, only with
Illustration illustrates the basic structure of the present invention, therefore it only shows composition related to the present invention.
Hereinafter, the present invention gives following embodiment and is described with reference to the drawings.However the present invention is not restricted to these implement
Example.The various values and material used in these embodiments are illustrative.Description carries out in the following order：
1st, according to the embodiment of the present invention the whole description of electrode material, electrode and half-cell
2nd, embodiment 1 (electrode material and electrode according to the embodiment of the present invention)
3rd, embodiment 2 (improvement of electrode material and electrode prepared in embodiment 1)
4th, embodiment 3 (variation of the electrode material in 2 and electrode according to an embodiment of the invention)
5th, embodiment 4 (variation of half-cell prepared in 2 according to an embodiment of the invention)
6th, embodiment 5 (variation of half-cell prepared in 3 according to an embodiment of the invention)
[whole description of electrode material according to the embodiment of the present invention, electrode and battery]
According to the embodiment of the present invention electrode material, in electrode and battery, Ti3C2Two-dimensional slice structural material,
The reversible embedded abjection of sodium ion can be realized in organic electrolyte system.
According to the embodiments of the present invention for including above-mentioned preferred embodiment, relative to the sodium ion of standard hydrogen electrode
The electroactive point position section of battery is 0-3V.
According to the preparation of the battery of the embodiments of the present invention including above-mentioned preferred embodiment and packaging technology：By institute
The two-dimensional slice structural material of preparation is electroactive material, with conductive agent acetylene black, binding agent Kynoar (PVDF) by matter
Measure ratio 8:1:1 mixing, with n-methyl-2-pyrrolidone (NMP) for solvent, is coated on after stirring evenly on copper foil of affluxion body, so
Dry 12h is spare in 110 DEG C of vacuum drying chamber afterwards.
According to the preparation of the electrode material of the embodiments of the present invention including above-mentioned preferred embodiment：Institute of the present invention
It is untreated street drug with chemical reagent.Multilayer two-dimension lamellar structure Ti3C2Preparation method： Ti3AlC2Accurately
It weighs 1g to pour into plastic bottle with cover, graduated cylinder measures the dense HF of 10mL (Nanjing Chemistry Reagent Co., Ltd., >=40.0%), delays
Slowly plastic bottle is poured into, covers bottle cap and 18h is stirred at room temperature, centrifuged, gained precipitation is washed with distilled water, vacuum drying chamber
80 DEG C of dry 12h, it is spare.
Embodiment 1
The electrode material prepared in embodiment 1 includes the Ti with the reversible embedded abjection ability of sodium ion3C2Two-dimensional slice
Structural material.
According to above-mentioned whole description multilayer two-dimension lamellar structure Ti3C2The preparation method of electrode material, electrode and half-cell,
Electrode material, electrode and the half-cell needed for embodiment 1 are prepared, it is spare.
Ti is characterized by scanning electron microscope3C2Micro-structure, scanning electron microscope used in the present invention is equal
For field emission scanning electron microscope (FESEM, LEO1430VP, Germany).Such as Fig. 1 a, b, c, shown in d, dense HF is etched
The Ti arrived3C2For irregular particle, each particle is made of the lamellar structure of class sandwich, there is clear boundary between piece and piece
Line.
The storage sodium activity of the test material, battery test apparatus used in the present invention are assessed by electro-chemical test
It is Land 2001A cell testers.It is the Ti of multilayer two-dimension lamellar structure shown in c such as Fig. 3 a, b3C2It is born as sodium-ion battery
The first circle charge and discharge for the half-cell that pole is assembled, cycle life and high rate performance figure.Its first circle specific discharge capacity is
153.2mAh g-1, first circle coulombic efficiency is only 47.91%；Second circle specific discharge capacity is 60.7mAh g-1, after cycle 50 is enclosed
Specific discharge capacity is 56.4mAh g-1；Current density is 50 mA g-1When, specific discharge capacity is 59.6mAh g-1, current density
Increase to 2000mA g-1When, specific discharge capacity is 26.7mAh g-1, current density is reduced to 50mA g-1, specific discharge capacity is extensive
56.9mAh g are arrived again-1。
Embodiment 2
The electrode material prepared in embodiment 2 includes processed with the reversible embedded abjection ability DMSO of sodium ion
Ti3C2Two-dimensional slice structural material.
According to the increased two-dimensional slice structure Ti of above-mentioned whole description interlamellar spacing3C2Electrode material, electrode and half-cell
Preparation method, prepare embodiment 2 needed for electrode material, electrode and half-cell, it is spare.
The increased two-dimensional slice structure Ti of interlamellar spacing is observed by scanning electron microscope3C2Micro-structure, such as Fig. 1 c, d
It is shown, compared with sample in embodiment 1, with the Ti of DMSO processing3C2Interlamellar spacing significantly become larger, occur between piece and piece notable
Slit.
The Ti of DMSO processing3C2Chemical property, first circle specific discharge capacity are 480.3mAh g-1, first circle coulombic efficiency is
43.81%；Second circle specific discharge capacity is 272mAh g-1, specific capacity is 201.8 mAh g after cycle 50 is enclosed-1；Current density
For 50mA g-1When, specific discharge capacity is 192.2mAh g-1, current density increases to 2000mA g-1When, specific discharge capacity is
47.9mAh g-1, current density is reduced to 50mA g-1, specific discharge capacity is restored to 174.5mAhg-1。
Embodiment 3
The present embodiment place different from embodiment 2 is to handle Ti using organic solvent DMF3C2, remaining and implementation
Example 2 is identical.
Embodiment 4
The electrode material prepared in embodiment 4 includes the Ti with DMSO with the reversible embedded abjection of sodium ion3C2Two dimension
Lamellar structure material.
According to the increased two-dimensional slice structure Ti of above-mentioned whole description interlamellar spacing3C2Electrode material, electrode preparation side
Method prepares electrode material, electrode needed for embodiment 4.Prepared electrode is anode, and sodium piece is used as to electrode, glass fibre
Film (GF/D whatman) is as diaphragm, the NaClO of 1mol/L4It is dissolved in propene carbonate (PC) and ethylene carbonate (EC)
With volume fraction 1：Make electrolyte in the solution of 1 mixing, be assembled into 2032 type button cells.
The first circle specific discharge capacity of battery is 434.6mAh g in embodiment 4-1, first circle coulombic efficiency is 38.57%；The
Two circle specific discharge capacities are 202.84mAh g-1, specific capacity is 185.8mAh g after cycle 50 is enclosed-1；Current density is 50mA g-1
When, specific discharge capacity is 172.9mAh g-1, current density increases to 2000 mA g-1When, specific discharge capacity is 26.5mAh g-1, current density is reduced to 50mA g-1, specific discharge capacity is restored to 174.5mAh g-1。
Embodiment 5
The present embodiment place different from embodiment 4 is to substitute DMSO processing Ti using organic solvent DMF3C2,
It is remaining same as Example 4.
Using above-mentioned desirable embodiment according to the present invention as enlightenment, by above-mentioned description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the content on specification, it is necessary to determine its technical scope according to right.
Claims (8)
1. a kind of sodium-ion battery negative material, it is characterised in that：The electrode material includes that there is sodium ion to be embedded in ability
Two-dimensional slice structure Ti3C2。
2. a kind of sodium-ion battery negative material according to claim 1, it is characterised in that：The Ti3C2By 10 layers with
Upper less than 50 layers lamellar structures are formed.
3. a kind of sodium-ion battery negative material according to claim 1, it is characterised in that：The Ti3C2Using DMSO
Or DMF is enlarged interlamellar spacing and lamella part lift-off processing.
A kind of 4. sodium-ion battery negative material according to claim 3, which is characterized in that the multilayer two-dimension lamella
Structure Ti3C2The processing that interlamellar spacing is enlarged using DMSO is specific as follows：
(1)Ti3AlC2Precise 1g is poured into plastic bottle with cover, and graduated cylinder measures the dense HF of 10mL and is poured slowly into plastic bottle, covers
18h is stirred at room temperature in bottle cap, centrifuges, and gained precipitation is washed with distilled water, 80 DEG C of vacuum drying chamber dry 12h is spare；
(2) by the Ti obtained by back3C218h is stirred at room temperature with DMSO, centrifuges, by precipitation absolute ethyl alcohol and distilled water
Repeatedly washing, the dry 12h of 80 DEG C of vacuum drying chamber.
5. a kind of sodium-ion battery negative material according to claim 1, it is characterised in that：The sodium-ion battery
Electro-chemical activity test point position section is 0-3V.
6. a kind of sodium-ion battery negative material according to claim 1, it is characterised in that：The electrode material is used as
The cathode of battery.
7. a kind of sodium-ion battery negative material as described in any one of claim 1-6 is in organic electrolyte system the following group
Dress up the application of sodium ion half-cell.
8. a kind of preparation method of sodium ion half-cell as claimed in claim 7, it is characterised in that：The method includes following
Step：With the Ti of two-dimensional slice structure3C2For electroactive material, mixed with conductive agent acetylene black, binding agent Kynoar, with
N-methyl-2-pyrrolidone is solvent, is coated on copper foil of affluxion body after stirring evenly, then in 110 DEG C of vacuum drying chamber
Middle dry 12h is spare.
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Cited By (7)
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| CN110048099A (en) * | 2019-03-28 | 2019-07-23 | 天津大学 | Electrode material of sodium-ion battery and its preparation method and application |
| CN110224127A (en) * | 2019-06-21 | 2019-09-10 | 燕山大学 | A kind of lithium ion battery negative material and its preparation method and application |
| CN110444730A (en) * | 2019-08-19 | 2019-11-12 | 中南大学 | A kind of preparation method and application of tridimensional network nanometer layer zinc load |
| CN110504440A (en) * | 2019-09-17 | 2019-11-26 | 肇庆市华师大光电产业研究院 | A kind of preparation method and applications of positive electrode of sodium-sulfur cell material |
| CN112279252A (en) * | 2020-09-18 | 2021-01-29 | 南京邮电大学 | Improve Ti2Method of C hydrogen storage Properties |
| CN114361570A (en) * | 2022-01-11 | 2022-04-15 | 山东大学 | Sodium battery and preparation method thereof |
| CN114725330A (en) * | 2022-03-04 | 2022-07-08 | 厦门大学 | Preparation method and application of two-dimensional titanium carbide-zinc oxide composite material |
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