CN108539197A - The preparation method of high magnification sodium-ion battery cathode porous graphite hard carbon - Google Patents
The preparation method of high magnification sodium-ion battery cathode porous graphite hard carbon Download PDFInfo
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- CN108539197A CN108539197A CN201810205647.6A CN201810205647A CN108539197A CN 108539197 A CN108539197 A CN 108539197A CN 201810205647 A CN201810205647 A CN 201810205647A CN 108539197 A CN108539197 A CN 108539197A
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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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- 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 preparation methods of high magnification sodium-ion battery cathode porous graphite hard carbon；Include mainly：Cross-linking reaction is carried out first with the cation of sodium alginate and the multivalent transition metal with catalyzed graphitization effect; then nano metal/carbon composite is prepared by the catalyzed graphitization method that is carbonized, acid cleaning process removal metallic catalyst particle is finally utilized to obtain the graphitization hard carbon cathode material with opposite ordered nano meso-hole structure.The present invention introduces uniform nano-pore by the method for being crosslinked pickling in hard carbon, and the graphite linings degree of order of mesopore surfaces carbon is improved by situ catalytic method for graphitizing, therefore the porous graphite hard carbon material prepared possesses good hole path and electric conductivity, it is more advantageous to quick insertion/abjection of sodium ion and electronics, there is high power capacity and powerful storage sodium characteristic.
Description
Technical field
The present invention relates to anode material of lithium-ion battery technical fields, and in particular to a kind of high magnification sodium-ion battery cathode
With the preparation method of porous graphite hard carbon.
Background technology
With the fast development of portable electronic device and new-energy automobile, lithium ion battery is because of its high-energy density, length
Cycle life, safe to use, advantages of environment protection have become most widely used energy storage device in global range.But
Tellurian elemental lithium reserves are very limited, and price is relatively high, therefore the future development of lithium ion battery is limited.At sodium and lithium
In same main group, there is similar electrochemical properties, and the earth rich reserves of sodium element, cheap, sodium ion electricity
Pond has become most potential lithium ion battery substitute.
The lithium ion battery negative material of business application is mainly graphite (theoretical capacity 372mAh/g) at present, and graphite relies on
Lithium ion intercalation/deintercalation in the carbon-coating of its long-range order stores electricity.But when graphite is applied in the negative of sodium-ion battery
When extremely middle, the capacity showed only has 30mAh/g, far from meeting business application.This is mainly due to the half of sodium ion
(0.102 nanometer) radius (0.076 nanometer) for being much larger than lithium ion of diameter, and the interlamellar spacing of graphite is 0.335 nanometer, is insufficient to make
Sodium ion is in the free deintercalation of interlayer.Hard carbon is that one kind being difficult to complete graphited carbon material, is mainly pyrolyzed by high molecular polymer
.Hard carbon is formed by the unordered stacking of graphite-like structure of some shortrange orders, and the unordered accumulation of these class graphite linings can also
Introduce a large amount of micropore (<2nm).The class graphite linings interlamellar spacing of hard carbon is typically larger than 0.37 nanometer, and sodium ion can be in class graphite
With deintercalation in nano-pore between layer by layer, therefore, hard carbon material shows higher capacity in the cathode of sodium-ion battery, approaches
300mAh/g has higher application potential.But the intrinsic disadvantage of hard carbon material is its structural disorder, poorly conductive, this meeting
Its capacity under high current is caused drastically to decline, high rate performance is poor.
Invention content
It is an object of the invention to overcome above-mentioned the shortcomings of the prior art, it is negative to provide a kind of high magnification sodium-ion battery
The preparation method of pole porous graphite hard carbon；Utilize the characteristic of sodium alginate and multivalent metal cation self-crosslinking in hard carbon
The carbonization structure of the hole path, electron-transport and sodium ion deintercalation that are suitable for ion transmission is introduced in material.Specially it is directed to sea
Alginic acid can form evenly dispersed " Egg-box " nanostructure with multivalent metal cation self-crosslinking, and it is in situ to be carbonized
It is transformed into the characteristic of nano metal/carbon composite construction, is carried out using sodium alginate and the metal cation for capableing of catalyzed graphitization
After cross-linking reaction, novel porous graphitization hard carbon is prepared using carbonization, acid cleaning process.It is this compared with traditional hard carbon material
There is equally distributed nanopore-channel inside porous graphite hard carbon material prepared by method, can be that the transmission of sodium ion carries
For convenient channel, and the degree of graphitization of hard carbon middle hole wall carbon prepared by this method greatly improves, graphite layers are away from suitable
In, it is suitable for the quick transmission of the deintercalation and electronics of sodium ion so that it still maintains high power capacity under high current.
The purpose of the present invention is achieved through the following technical solutions：
The present invention relates to a kind of preparation method of high magnification sodium-ion battery cathode porous graphite hard carbon, including it is as follows
Step：
S1, using the cation of sodium alginate and the multivalent transition metal with catalyzed graphitization effect be crosslinked instead
It answers；
S2, by being carbonized, catalyzed graphitization method prepares corresponding nano metal/carbon composite；
S3, the metallic catalyst particle in the nano metal/carbon composite is removed using acid cleaning process, obtained
Graphitization hard carbon cathode material with opposite ordered nano meso-hole structure
Preferably, the cross-linking reaction is specially：Sodium alginate is dissolved in water, it is 0.2-10% to be made into mass concentration
Solution；Sodium alginate soln is added in the multivalent transition metal salting liquid that mass concentration is 1-20% again and be crosslinked instead
It answers, the reaction time is 24 hours.
Preferably, the multivalent transition metal be with catalyzed graphitization effect and metal activity series it is more before hydrogen
One or more of valence transition metal.
Preferably, the cation of the multivalent transition metal is Co2+、Ni2+、Fe3+、Fe2+、Ca2+、Mn2+、Sn2+、Sn4+In
One or more.
Preferably, the cation of the guluronic acid polymer segment in sodium alginate and multivalent transition metal is selfed
Connection reaction forms uniform " egg-box " nano hybridization structure in sodium alginate matrix.
Preferably, the step S1 further includes the carbonization pre-treatment to cross-linking products：By sodium alginate and multivalent transition gold
Freeze-drying 1-3 days after the cross-linking products of the cation of category are cleaned 1-5 times with deionized water.
Preferably, the carbonization catalyzed graphitization method is specially：Calcining 0.5-12 is small under atmosphere of inert gases protection
When, calcination temperature is 600-1800 DEG C.
Preferably, the structure of the nano metal/carbon composite is specially：3-50 nanometers of metallic particles is uniformly distributed
2-100 layers of graphitization carbon-coating are wrapped in carbon base body, and around metallic particles.Under the preparation process condition of the present invention,
During carbonization, the cross-linking products of sodium alginate and metal cation are changed into nano metal/carbon composite, herein mistake
Cheng Zhong, sodium alginate macromolecule are thermally cracked to produce the carbon materials of high-carbon content and by metal cation in-situ reducing at corresponding
Metal nanoparticle, is dissolved then in the carbon around metal nanoparticle in metal nanoparticle lattice and mistake at high temperature
It is saturated indigenous graphite layer again, the graphite linings of package are formed on metal nanoparticle periphery, to improve the graphitization of carbon base body
Degree.
Preferably, the pickling is specially：The nano metal of gained/carbon composite is added in strong acid solution, 40-90
DEG C heating and magnetic agitation 2-24 hour, later filter sample, it is 7 to be cleaned repeatedly with deionized water to pH, forced air drying.
Preferably, it is graphitized main micropore in hard carbon cathode material and concentrates on 0.3-50 nanometers with mesoporous pore diameter range.
Preferably, in the matrix of the graphitization hard carbon cathode material with opposite ordered nano meso-hole structure
Even nanopore-channel, and have the 2-100 graphitization carbon-coatings that spacing is 0.37-0.42 nanometers layer by layer on hole wall.
Compared with prior art, the present invention has the advantages that：
(1) present invention uses sodium alginate for raw material, by being crosslinked, be carbonized with metal cation, then washes away metal
The method of grain, uniform nanopore-channel is introduced in common sodium alginate hard carbon material.In addition, by sodium alginate and gold
When belonging to the cross-linking products carbonization of cation, metallic particles therein can play the role of catalyzed graphitization, in common seaweed
Graphitization carbon-coating structure is introduced in sour sodium hard carbon material, improves the electric conductivity of material.
(2) when porous graphite hard carbon prepared by the present invention being applied in the cathode of sodium-ion battery, nanometer therein
Hole path can provide express passway for the transmission of sodium ion, and graphitization carbon-coating structure therein is also beneficial to sodium ion and electricity
The quick transmission of son, therefore this porous graphite hard carbon can show high power capacity under high current.
(3) step of the present invention is simple, easy to operate, with obvious effects, has good application prospect.
Description of the drawings
Upon reading the detailed description of non-limiting embodiments with reference to the following drawings, other feature of the invention,
Objects and advantages will become more apparent upon：
Fig. 1 is the transmission electron microscope of nanometer cobalt/carbon composite of 1 gained of embodiment and porous graphite hard carbon in the present invention
Photo；Wherein, a be bar=50nm nanometer cobalt/carbon composite transmission electron microscope photo, b be bar=5nm nanometer cobalt/
The transmission electron microscope photo of carbon composite, c are the transmission electron microscope photo of the porous graphite hard carbon of bar=20nm, d bar=
The transmission electron microscope photo of the porous graphite hard carbon of 5nm；
Fig. 2 is the X ray diffracting spectrum of the porous graphite hard carbon of 1 gained of embodiment in the present invention；
Fig. 3 is the Raman collection of illustrative plates of the porous graphite hard carbon of 1 gained of embodiment in the present invention；
Fig. 4 is the nitrogen adsorption desorption curve of the porous graphite hard carbon of 1 gained of embodiment in the present invention；
Fig. 5 is the graph of pore diameter distribution of the porous graphite hard carbon of 1 gained of embodiment in the present invention；
Fig. 6 is high rate performance of the porous graphite hard carbon of 1 gained of embodiment in the present invention in sodium-ion battery cathode.
Fig. 7 is the transmission electron microscope photo of the porous graphite hard carbon of 2 gained of embodiment in the present invention, wherein a bar=
The transmission electron microscope photo of the porous graphite hard carbon of 50nm, the transmission electron microscope photo of the porous graphite hard carbon of bar=5nm.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1
The present embodiment is related to a kind of preparation method of high magnification sodium-ion battery cathode porous graphite hard carbon, including such as
Lower step：
(1) cross-linking reaction：25g sodium alginates are dissolved in 975mL deionized waters, it is 2.5% to be configured to mass fraction
Solution.50g cobalt nitrates are dissolved in 950mL deionized waters, the solution that mass fraction is 5% is configured to.By sodium alginate soln
It is slowly added dropwise into cobalt nitrate solution, the volume ratio of sodium alginate soln and cobalt nitrate solution is 4：5.24 hours are stood, is waited for
Cross-linking reaction is fully completed.The alginic acid cobalt of crosslinking gained is soaked in deionized water, is cleaned repeatedly three times, removal surface is not
It is freeze-dried 24 hours after participating in the cobalt ions of cross-linking reaction.
(2) it is carbonized：Alginic acid acid cobalt after freeze-drying is transferred in tube furnace, under nitrogen atmosphere, according to 5 DEG C/minute
The rate of clock is warming up to 800 DEG C, and keeps the temperature 1 hour.Carbonization obtains nanometer cobalt/carbon composite.
(3) pickling：The nanometer cobalt of carbonization gained/carbon composite is added in 1L hydrochloric acid solutions (2mol/L), 60 DEG C add
Hot simultaneously magnetic agitation 12 hours, later filter sample, and it is 7 to be cleaned repeatedly with deionized water to pH, by sample forced air drying.
Implementation result：
Nanometer cobalt/carbon composite obtained by according to the method described above is as shown in figure 1 a-b, it can be seen that 5-10 rans
Metal cobalt granule be evenly distributed in carbon base body.The porous graphite hard carbon material of gained can be seen as shown in Fig. 1 c-d
To having a large amount of uniform nanopore-channels in carbon base body, and it is 0.38 nanometer of graphite to have 10 layers or so interlamellar spacings on hole wall
Change carbon-coating.The X-ray diffractogram and Raman ray diagram of the porous graphite hard carbon material are shown in Fig. 2,3, show higher graphite
Change degree.The nitrogen adsorption desorption curve and pore distribution curve of the material are shown in Fig. 4,5, show its nano-porous structure.Take 0.1g
The porous graphite hard carbon, according to 1:1:8 mass ratio addition test material, conductive black, (Kynoar is dissolved in binder
In N-Methyl pyrrolidone) slurry is stirred into, slurry is evenly coated on copper foil, the electrode slice of diameter 11mm is cut to after dry.
It is to electrode, using glass fibre as diaphragm, with 1mol/L sodium perchlorate solutions with metallic sodium piece in the glove box of argon atmosphere
(solvent is ethylene carbonate and propene carbonate 1：1) it is electrolyte, electrode slice is assembled into the half-cell of CR2032 types.It should
Half-cell carries out charge and discharge, cyclic voltammetric, ac impedance measurement.Fig. 6 is the high rate performance figure of the porous graphite hard carbon material,
Specific capacity when current density is 0.05A/g is 275mAh/g, and specific capacity is 131mAh/g under the high current of 5A/g.
Embodiment 2
The present embodiment is related to a kind of preparation method of high magnification sodium-ion battery cathode porous graphite hard carbon, including such as
Lower step：
(1) 2g sodium alginates are taken to be dissolved in 998mL deionized waters, the solution that configuration quality score is 0.2%.Take 25g nitre
Sour nickel is dissolved in 975mL deionized waters, the solution that configuration quality score is 2.5%.Sodium alginate soln is placed in spray bottle and is delayed
Slowly it is sprayed onto in nickel nitrate solution, obtains alginic acid nickel gel film.Repeatedly with deionized water by alginic acid nickel gel film
Cleaning three times, is freeze-dried 24 hours.
(2) dry alginic acid nickel is taken, is put into tube furnace, is passed through argon gas, 1200 are warming up to 10 DEG C/min of speed
DEG C, and 12 hours are kept the temperature, it is taken out after natural cooling, obtains nano nickel/carbon composite.
(3) nano nickel/carbon composite is added in 1L hydrochloric acid solutions (2mol/L), simultaneously magnetic agitation 12 is small for 60 DEG C of heating
When, sample is filtered later, it is 7 to be cleaned repeatedly with deionized water to pH, by sample forced air drying.
Implementation result：Prepared porous graphite hard carbon material structure is as shown in fig. 7, maintain more according to the method described above
Pore property and graphitization characteristic.And since carburizing temperature is higher (1200 DEG C), the hard carbon material carbonization structure of gained is complete,
With 50 layers or so graphitization carbon-coatings, there is outstanding electric conductivity.The 0.1g porous graphite hard carbons are taken, according to 1:1:8 matter
Amount stirs into slurry than test material, conductive black, binder (Kynoar is dissolved in N-Methyl pyrrolidone) is added, and will starch
Material is evenly coated on copper foil, and the electrode slice of diameter 11mm is cut to after dry.In the glove box of argon atmosphere, with metallic sodium piece
For to electrode, using glass fibre as diaphragm, using 1mol/L sodium perchlorate solutions, (solvent is ethylene carbonate and propene carbonate 1：
1) it is electrolyte, electrode slice is assembled into the half-cell of CR2032 types.The half-cell is subjected to charge and discharge, cyclic voltammetric, exchange
Testing impedance.The porous graphite hard carbon material shows outstanding high rate performance.
Embodiment 3
The present embodiment is related to a kind of preparation method of high magnification sodium-ion battery cathode porous graphite hard carbon, including such as
Lower step：
(1) 100g sodium alginates are taken to be dissolved in 900mL deionized waters, the solution that configuration quality score is 10%.Take 100g
Ferric nitrate is dissolved in 900mL deionized waters, the solution that configuration quality score is 10%.By sodium alginate soln and iron nitrate solution
According to 1:1 mass ratio mixing.Obtained ferric alginate gel is cleaned three times repeatedly with deionized water, freeze-drying 24 is small
When.
(2) dry ferric alginate is taken, is put into tube furnace, argon gas is passed through, 1000 are warming up to 10 DEG C/min of speed
DEG C, and 12 hours are kept the temperature, it is taken out after natural cooling, obtains Nanoscale Iron/carbon composite.
(3) nano nickel/carbon composite is added in 1L hydrochloric acid solutions (2mol/L), simultaneously magnetic agitation 12 is small for 60 DEG C of heating
When, sample is filtered later, it is 7 to be cleaned repeatedly with deionized water to pH, by sample forced air drying.
Implementation result：Prepared porous graphite hard carbon material according to the method described above, maintains porosity characteristic and graphite
Change characteristic.The 0.1g porous graphite hard carbons are taken, according to 1:1:Test material, conductive black, binder is added in 8 mass ratio
(Kynoar is dissolved in N-Methyl pyrrolidone) stirs into slurry, and slurry is evenly coated on copper foil, is cut to after dry straight
The electrode slice of diameter 11mm.In the glove box of argon atmosphere, with metallic sodium piece be to electrode, using glass fibre as diaphragm, with
(solvent is ethylene carbonate and propene carbonate 1 to 1mol/L sodium perchlorate solutions：1) it is electrolyte, electrode slice is assembled into
The half-cell of CR2032 types.The half-cell is subjected to charge and discharge, cyclic voltammetric, ac impedance measurement.The porous graphite hard carbon
Material shows good high rate performance.
Specific embodiments of the present invention are described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (10)
1. a kind of preparation method of high magnification sodium-ion battery cathode porous graphite hard carbon, which is characterized in that the method
Include the following steps：
S1, cross-linking reaction is carried out using the cation of sodium alginate and the multivalent transition metal with catalyzed graphitization effect；
S2, by being carbonized, catalyzed graphitization method prepares corresponding nano metal/carbon composite；
S3, the metallic catalyst particle in the nano metal/carbon composite is removed using acid cleaning process, is had
The graphitization hard carbon cathode material of opposite ordered nano meso-hole structure.
2. the preparation method of high magnification sodium-ion battery cathode porous graphite hard carbon according to claim 1, special
Sign is that the multivalent transition metal is the multivalent transition gold before hydrogen with catalyzed graphitization effect and metal activity series
One or more of belong to.
3. the preparation method of high magnification sodium-ion battery cathode porous graphite hard carbon according to claim 1, special
Sign is that the cation of the multivalent transition metal is Co2+、Ni2+、Fe3+、Fe2+、Ca2+、Mn2+、Sn2+、Sn4+In one kind or
It is several.
4. the preparation method of high magnification sodium-ion battery cathode porous graphite hard carbon according to claim 1, special
Sign is that the cation generation self-crosslinking of the guluronic acid polymer segment in sodium alginate and the multivalent transition metal is anti-
It answers, forms uniform " Egg-box " nano hybridization structure in sodium alginate matrix.
5. the preparation method of high magnification sodium-ion battery cathode porous graphite hard carbon according to claim 1, special
Sign is that the step S1 further includes the steps that carrying out carbonization pre-treatment to cross-linking products；The pre-treatment is by sodium alginate
Freeze-drying 1-3 days after being cleaned 1-5 times with deionized water with the cross-linking products of the cation of multivalent transition metal.
6. the preparation method of high magnification sodium-ion battery cathode porous graphite hard carbon according to claim 1, special
Sign is that the carbonization catalyzed graphitization method is specially：It is calcined 0.5-12 hours under atmosphere of inert gases protection, calcining temperature
Degree is 600-1800 DEG C.
7. the preparation method of high magnification sodium-ion battery cathode porous graphite hard carbon according to claim 1, special
Sign is that the structure of the nano metal/carbon composite is specially：3-50 nanometers of metallic particles is evenly distributed on carbon base body
In, and 2-100 layers of graphitization carbon-coating are wrapped in around metallic particles.
8. the preparation method of high magnification sodium-ion battery cathode porous graphite hard carbon according to claim 1, special
Sign is that the pickling is specially：Nano metal obtained by step S2/carbon composite is added in strong acid solution, 40-90 DEG C
Simultaneously magnetic agitation 2-24 hours are heated, later filter sample, it is 7 to be cleaned repeatedly with deionized water to pH, forced air drying.
9. the preparation method of high magnification sodium-ion battery cathode porous graphite hard carbon according to claim 1, special
Sign is that main micropore concentrates on 0.3-50 nanometers with mesoporous pore diameter range in the graphitization hard carbon cathode material.
10. the preparation method of high magnification sodium-ion battery cathode porous graphite hard carbon according to claim 1, special
Sign is, with uniform nanometer in the matrix of the graphitization hard carbon cathode material with opposite ordered nano meso-hole structure
Hole path, and have the 2-100 graphitization carbon-coatings that spacing is 0.37-0.42 nanometers layer by layer on hole wall.
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| CN109346332A (en) * | 2018-10-17 | 2019-02-15 | 上海交通大学 | Lithium ion mixed capacitor and preparation method thereof based on alginic acid cross-linked structure |
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| CN111146424B (en) * | 2019-12-30 | 2023-06-06 | 上海交通大学 | Metal sulfide/carbon composite material, and preparation method and application thereof |
| CN112174130A (en) * | 2020-09-30 | 2021-01-05 | 福建海峡石墨烯产业技术研究院有限公司 | Preparation method of crosslinked thin-layer graphite serving as negative electrode of potassium ion battery |
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| CN113023705A (en) * | 2021-02-05 | 2021-06-25 | 江苏大学 | Preparation method of hydrogen-rich carbon material and application of hydrogen-rich carbon material in lithium-sodium-potassium energy storage |
| CN114380284A (en) * | 2022-01-12 | 2022-04-22 | 河北坤天新能源科技有限公司 | Hard carbon negative electrode material and preparation method and application thereof |
| CN115832232A (en) * | 2022-01-13 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Negative electrode active material, negative electrode sheet, secondary battery, battery module, battery pack, and electric device using same |
| CN115832232B (en) * | 2022-01-13 | 2023-10-20 | 宁德时代新能源科技股份有限公司 | Negative electrode active material, negative electrode sheet, secondary battery, battery module, battery pack, and power device |
| CN114373928A (en) * | 2022-01-24 | 2022-04-19 | 天津大学 | High-energy-density sodium ion battery |
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| CN115124025A (en) * | 2022-08-16 | 2022-09-30 | 中国石油大学(华东) | Hard carbon material, preparation method thereof and application thereof in sodium-ion battery |
| CN115417398A (en) * | 2022-08-30 | 2022-12-02 | 北京理工大学长三角研究院(嘉兴) | High-first-efficiency hard carbon cathode for sodium ion battery |
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