CN114975979A - C/G/CNT-S negative electrode material, preparation method and application - Google Patents
C/G/CNT-S negative electrode material, preparation method and application Download PDFInfo
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- CN114975979A CN114975979A CN202210796544.8A CN202210796544A CN114975979A CN 114975979 A CN114975979 A CN 114975979A CN 202210796544 A CN202210796544 A CN 202210796544A CN 114975979 A CN114975979 A CN 114975979A
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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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/44—Methods for charging or discharging
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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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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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 provides a C/G/CNT-S negative electrode material, a preparation method and application, and particularly relates to the technical field of lithium ion batteries. The C/G/CNT-S negative electrode material comprises carbon fibers, a sulfur inner core, a graphene box and carbon nanotubes; the graphene box arrays are arranged on the surface of the carbon fiber; the sulfur core is located inside the graphene box; the carbon nano tube is positioned on the surface of the graphene box and is bonded with the graphene box in a C-C bonding mode. The graphene box is used as a buffer space for volume expansion in the charging and discharging processes of the sulfur cathode, and provides compact outer layer protection for sulfur, so that the falling of the sulfur is effectively prevented; the graphene box is bonded with the carbon nano tube to form a stable structure, so that the conductivity of the cathode material is improved. The integrated C/G/CNT-S cathode material perfectly builds a 3D conductive network, improves the conductivity and stability of the whole cathode material, and further improves the electrical property.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a C/G/CNT-S negative electrode material, a preparation method and application.
Background
Sulfur has a theoretical capacity of up to 1675mAh/g, and is a very potential lithium ion battery negative electrode candidate material, but sulfur has two major obstacles as a lithium ion negative electrode material: poor conductivity and volume expansion, and therefore, the commercial application of sulfur as a lithium ion negative electrode material still needs to be further improved and researched.
In increasing sulfur conductivity, it is common practice to compound with highly conductive carbon materials to increase the electron conductivity of sulfur, SP 2 The hybrid two-position graphene material and the one-dimensional carbon nanotube material are excellent in conductivity in carbon materials and can be used as modified materials for improving sulfur conductivity; in terms of volume expansion problem in the charging and discharging process, a special structure is usually constructed, and enough expansion buffer space is reserved.
Aiming at the modification design, people develop various modification means such as loading, doping, core-shell structure construction and the like, and generally the large-scale application cannot be realized due to factors such as complex process, low efficiency, high cost and the like. According to the traditional conductive composite carbon material, reduced graphene oxide or carbon nano tubes are used for constructing a conductive network through physical mixing, sulfur is loaded on the surfaces of the graphene and the carbon nano tubes, the loading strength is usually weak, and the carbon material is used as a negative electrode material and is easy to fall off after multiple cycles, so that the capacity of a battery is attenuated.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a C/G/CNT-S negative electrode material to solve the technical problems of poor conductivity and volume expansion of a sulfur negative electrode material and battery capacity attenuation caused by easy shedding of sulfur loaded on the surfaces of graphene and carbon nano tubes in the prior art.
The second purpose of the invention is to provide a preparation method of the C/G/CNT-S negative electrode material, so as to relieve the technical problems of complex process, low efficiency and high cost of the conductive composite carbon material preparation in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides a C/G/CNT-S negative electrode material, which comprises a carbon fiber, a sulfur inner core, a graphene box and a carbon nano tube;
the graphene box arrays are arranged on the surface of the carbon fiber;
the sulfur core is located inside the graphene box;
the carbon nano tube is positioned on the surface of the graphene box and is bonded with the graphene box in a C-C bonding mode.
The second aspect of the present invention provides a method for preparing a C/G/CNT-S anode material, comprising the steps of:
step A: uniformly mixing soluble salt of transition metal, a catalytic growth source, a chelating agent and a pH value regulator to obtain a first solution;
and B: pouring the first solution into a container with carbon fiber cloth, and transferring the container to a reaction kettle for reaction to obtain a G @ metal compound;
and C: transferring the G @ metal compound to a single-temperature-zone tube furnace, heating in a protective gas atmosphere, and introducing a carbon source gas to grow graphene to obtain a C/G @ metal compound;
step D: respectively carrying out acid-base treatment on the C/G @ metal compound, drying, and then carrying out CO treatment 2 And N 2 Carrying out heat treatment in mixed atmosphere, acid water bath treatment, washing and secondary drying to obtain C/G/CNT;
step E: and uniformly scattering sulfur powder on the surface of the C/G/CNT, and preserving heat in an inert atmosphere to obtain the C/G/CNT-S negative electrode material.
Optionally, the soluble salt of a transition metal comprises a soluble salt of nickel.
Preferably, the soluble salt of nickel comprises at least one of nickel nitrate, nickel chloride and nickel sulfate.
Preferably, the catalytic growth source comprises ferric nitrate.
Preferably, the chelating agent comprises 5-sulfosalicylic acid.
Preferably, the pH adjuster comprises at least one of urea, sodium hydroxide, and ammonia.
Optionally, the molar ratio of the soluble salt of the transition metal, the catalytic growth source and the pH adjuster is 4: (0.2-1.5): (0.8-4.5).
Preferably, the chelating agent is added in an amount of the sum of the moles of the soluble salt of the transition metal and the catalytic growth source.
Alternatively, in step B, the temperature of the reaction is between 80 ℃ and 150 ℃.
Preferably, in step B, the reaction time is 4h-24 h.
Preferably, the step B further comprises washing after the reaction and drying again to obtain the metal compound.
Preferably, the temperature of the secondary drying is 60-100 ℃.
Optionally, in the step C, the temperature rise rate is 2 ℃/min to 5 ℃/min.
Preferably, the temperature after the temperature rise is 900-1100 ℃.
Preferably, the carbon source gas comprises ethylene.
Preferably, the carbon source gas is introduced at a rate of 200ml/min to 500 ml/min.
Preferably, the time for growing the graphene is 10min to 30 min.
Optionally, in step D, the temperature of the heat treatment is 700 ℃ to 900 ℃.
Preferably, the time of the heat treatment is 0.2h-1 h.
Optionally, in step E, the temperature of the incubation is 130 ℃ to 200 ℃.
Preferably, in the step E, the heat preservation time is 12h-24 h.
Alternatively, in step E, the acid water bath treatment is performed using an HCI solution.
Preferably, the concentration of the HCI solution is between 0.5M and 2M.
Preferably, the time of the acid water bath treatment is 0.5h-2 h.
The third aspect of the invention provides the application of the C/G/CNT-S negative electrode material in a lithium ion battery.
Compared with the prior art, the invention has at least the following beneficial effects:
in the C/G/CNT-S cathode material provided by the invention, the carbon fiber provides a loading substrate for the growth of a graphene box structure, and the growth of the graphene box structure is facilitated; the graphene box is used as a buffer space for volume expansion in the charging and discharging processes of the sulfur cathode, so that crushing and collapse caused by insufficient volume expansion space of sulfur are prevented; the sulfur is positioned inside the graphene box, the graphene box provides compact outer layer protection for the sulfur, and the sulfur is effectively prevented from falling off; the graphene box is bonded with the carbon nano tube to form a stable structure, so that the conductivity of the cathode material is improved. The integrated C/G/CNT-S cathode material perfectly builds a 3D conductive network, so that the conductivity and stability of the whole cathode material are improved, and the electrical property is further improved.
The preparation method of the C/G/CNT-S cathode material provided by the invention obtains the material by establishing a template, growing and etching the template. The preparation method has the advantages of continuous process, strong controllability, accurate regulation and control of the box-shaped structure of the graphene, realization of fitting and coating of sulfur, easy popularization and contribution to large-scale industrial production.
The C/G/CNT-S negative electrode material provided by the invention contributes to extremely high volume specific capacity for the lithium ion battery, so that the volume energy density of the lithium ion battery is greatly improved, and the lithium ion battery becomes smaller. And the obtained lithium ion battery has high reversible specific capacity and good capacity retention rate, and is suitable for large-scale popularization and use.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a carbon fiber substrate provided with LDHs growth in example 1;
FIG. 2 is a Fe-doped carbon fiber-loaded substrate growth of example 1Hetero alpha-Ni (OH) 2 The LDHs template of (1);
FIG. 3 is a sample of C-G @ FeNi-LDHs grown with graphene of example 1;
FIG. 4 is a sample of C-G-CNT after etching LDHs templates of example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. The components of embodiments of the present invention may be arranged and designed in a wide variety of different configurations.
The invention provides a C/G/CNT-S negative electrode material, which comprises carbon fibers, a sulfur core, a graphene box and carbon nanotubes;
the graphene box arrays are arranged on the surface of the carbon fiber;
the sulfur core is located inside the graphene box;
the carbon nano tube is positioned on the surface of the graphene box and is bonded with the graphene box in a C-C bonding mode.
In the C/G/CNT-S cathode material provided by the invention, the carbon fiber provides a loading substrate for the growth of a graphene box structure, and the growth of the graphene box structure is facilitated; the graphene box is used as a buffer space for volume expansion in the charging and discharging processes of the sulfur cathode, so that crushing and collapse caused by insufficient volume expansion space of sulfur are prevented; the sulfur is positioned inside the graphene box, the graphene box provides compact outer layer protection for the sulfur, and the sulfur is effectively prevented from falling off; the graphene box is bonded with the carbon nano tube to form a stable structure, so that the conductivity of the cathode material is improved. The integrated C/G/CNT-S cathode material perfectly builds a 3D conductive network, improves the conductivity and stability of the whole cathode material, and further improves the electrical property.
The second aspect of the present invention provides a method for preparing a C/G/CNT-S anode material, comprising the steps of:
step A: uniformly mixing soluble salt of transition metal, a catalytic growth source, a chelating agent and a pH value regulator to obtain a first solution;
the soluble salt of the transition metal is chosen because the growth of graphene generally requires a relatively smooth substrate, preferably a micron or submicron sheet with a certain thickness, which cannot be stacked layer by layer in order to fully utilize the growth area. The soluble salt of the transition metal and the catalytic growth source can generate transition metal double hydroxide under the action of the pH value regulator.
The transition metal double hydroxide generally presents a sheet structure, the surface is smooth and fine, and the layered transition metal hydroxide (LDHs) is an ideal substrate for growing the box-shaped graphene nanoplatelets. The LDHs material is simple to prepare, the metal source can be selected widely, and the carbon nano obtained by doping the iron source can obtain the catalytic site for the growth of the CNT on the surface of the LDHs. Because the iron source for the catalytic growth of the CNT tube is small in size, and the thermal stability of the iron source is difficult to maintain under high-temperature conditions, the invention obtains the small-size iron source for the in-situ catalytic growth of the thermally stable CNT by a doping compounding way. Common LDHs are mainly prepared by hydrothermal methods, and the samples are generated in a precipitated form, which often makes it difficult to obtain samples that grow in a regular arrangement.
And B, step B: and pouring the first solution into a container with carbon fiber cloth, and transferring the container to a reaction kettle for reaction to obtain the G @ metal compound.
In some embodiments of the present invention, the carbon fiber cloth preferably has a thickness of 1 μm to 50 μm, and is pre-treated for reuse. During pretreatment, the carbon fiber cloth is immersed in a nitric acid solution for pretreatment for 0.5 to 5 hours at the temperature of between 60 and 150 ℃, and then is washed by deionized water for multiple times until the pH value is neutral. The method aims to remove organic impurities on the surface of the carbon fiber cloth and activate the carbon fiber cloth, so that the carbon fiber cloth has better loading capacity and helps the LDHs material to nucleate and vertically grow. The carbon fiber cloth pretreated by nitric acid is used as a load substrate, and compared with the traditional substrate-free hydrothermal preparation process, the LDHs which are orderly arranged and vertically grow can be obtained.
G @ metal composite is micron LDHs with vertically grown carbon fiber cloth surface arrays.
And C: and transferring the G @ metal compound to a single-temperature-zone tube furnace, heating in a protective gas atmosphere, and introducing a carbon source gas to grow graphene to obtain the C/G @ metal compound.
In some embodiments of the invention, the shielding gas is typically, but not limited to, nitrogen or argon.
The C/G @ metal compound is a substance with graphene growing on the surface of LDHs.
Step D: respectively carrying out acid-base treatment on the C/G @ metal compound, drying, and then carrying out CO treatment 2 And N 2 And carrying out heat treatment in a mixed atmosphere, acid water bath treatment, washing and secondary drying to obtain the C/G/CNT.
The C/G @ metal complex is subjected to acid-base treatment respectively in order to remove alpha-Ni (OH) 2 And (5) template.
CO 2 And N 2 The reason why the heat treatment in the mixed atmosphere and the secondary acid-base treatment are performed is to generate a residual Fe catalyst source for the CNT.
And E, step E: and uniformly scattering sulfur powder on the surface of the C/G/CNT, and preserving heat in an inert atmosphere to obtain the C/G/CNT-S negative electrode material.
And E, the purpose of the step E is to enable sulfur to permeate into the box-shaped graphene nanoplatelets through hot melting diffusion, and compared with the traditional load, the step E has more ideal coating performance.
The preparation method of the C/G/CNT-S cathode material provided by the invention obtains the material by establishing a template, growing and etching the template. The preparation method has the advantages of continuous process, strong controllability, accurate regulation and control of the box-shaped structure of the graphene, realization of fitting and coating of sulfur, easy popularization and contribution to large-scale industrial production.
Optionally, the soluble salt of a transition metal comprises a soluble salt of nickel.
Preferably, the soluble salt of nickel comprises at least one of nickel nitrate, nickel chloride and nickel sulfate.
Hydroxide of nickel alpha-Ni (OH) 2 The LDHs template which is vertically grown and arranged on the surface of the carbon fiber cloth in an array mode can be obtained by loading nucleation growth on the surface of the carbon fiber cloth after pretreatment, and meanwhile Ni is good catalyst for growth of grapheneAnd (4) source melting.
Preferably, the catalytic growth source comprises ferric nitrate.
As a catalytic growth source, ferric nitrate promotes in-situ growth of Carbon Nanotubes (CNT), and Fe is doped in nickel hydroxide alpha-Ni (OH) 2 And the doping is carried out to obtain a small-size thermally stable CNT catalytic growth source, so that the method provides help for building an ideal 3D conductive network for the subsequent graphene/carbon nano tube.
Preferably, the chelating agent comprises 5-sulfosalicylic acid.
5-sulfosalicylic acid acts as a chelator for the growth of LDHs because 5-sulfosalicylic acid can form complexes with transition metal ions and metal ions in the catalytic growth source in aqueous solution.
Preferably, the pH adjuster comprises at least one of urea, sodium hydroxide, and ammonia.
In a preferred embodiment of the present invention, the pH adjusting agent is urea, since urea can hydrolyze under high temperature conditions to produce ammonia, which can provide an alkaline environment for the growth of LDHs. Meanwhile, the urea hydrolysis reaction is very slow, the supersaturation degree of LDHs crystal precipitation is very low, the nucleation speed of LDHs is slow, the improvement of the crystallinity of the LDHs material is facilitated, the LDHs template with micron/submicron-scale large sheet diameter is obtained, and the sheet diameter of the LDHs template is easy to control.
Optionally, the molar ratio of the soluble salt of the transition metal, the catalytic growth source and the pH adjuster is 4: (0.2-1.5): (0.8-4.5).
In some embodiments of the invention, the molar ratio of soluble salt of transition metal, catalytic growth source, and pH adjuster is typically, but not limited to, 4:0.2:0.8, 4:0.2:4.5, 4:1.5:0.8, 4:1.5:4.5, 4:0.8:0.8, 4:0.8:4.5, 4:0.8:2.5, or 4:0.8: 2.5.
In some embodiments of the present invention, microstructures with different morphologies can be obtained by adjusting the types and addition ratios of the metal in the soluble salt of the transition metal and the catalytic growth source.
Preferably, the chelating agent is added in an amount of the sum of the moles of the soluble salt of the transition metal and the catalytic growth source.
Alternatively, in step B, the temperature of the reaction is between 80 ℃ and 150 ℃.
In some embodiments of the invention, the temperature of the reaction is typically, but not limited to, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃.
Preferably, in step B, the reaction time is 4-24 h.
In some embodiments of the invention, the reaction time is typically, but not limited to, 4h, 8h, 12h, 16h, 20h, or 24 h.
Preferably, the step B further comprises washing after the reaction and drying again to obtain the metal compound.
Preferably, the temperature of the secondary drying is 60-100 ℃.
The washing after the reaction is to remove the reaction residue remained on the surface of the LDHs template. In some embodiments of the present invention, the temperature of the re-drying is typically, but not limited to, 60 ℃, 70 ℃, 80 ℃, 90 ℃ or 100 ℃.
Optionally, in the step C, the temperature rise rate is 2 ℃/min to 5 ℃/min.
In some embodiments of the invention, the rate of temperature increase is typically, but not limited to, 2 deg.C/min, 3 deg.C/min, 4 deg.C/min, or 5 deg.C/min.
Preferably, the temperature after the temperature rise is 900-1100 ℃.
In some embodiments of the invention, the post-ramp temperature is typically, but not limited to, 900 ℃, 1000 ℃, or 1100 ℃.
Preferably, the carbon source gas comprises ethylene.
The carbon source gas has high solubility of carbon atoms in Ni, when graphene is grown on a Ni substrate, the carbon atoms are dissolved in Ni in a large amount at high temperature and are randomly distributed in Ni, and when the temperature is reduced, the carbon atoms are precipitated at the grain boundary of Ni and then nucleate and grow on the surface of hydroxide to grow into graphene blocky areas, and the blocky areas are connected with each other along with the increase of the growth time to generate single-layer or multi-layer graphene.
Preferably, the carbon source gas is introduced at a rate of 200ml/min to 500 ml/min.
In some embodiments of the invention, the carbon source gas is typically introduced at a rate of, but not limited to, 200ml/min, 300ml/min, 400ml/min, or 400 ml/min.
Preferably, the time for growing the graphene is 10min to 30 min.
Optionally, in step D, the temperature of the heat treatment is 700 ℃ to 900 ℃.
In some embodiments of the invention, in step D, the temperature of the heat treatment is typically, but not limited to, 700 ℃, 800 ℃ or 900 ℃.
Preferably, the time of the heat treatment is 0.2h-1 h.
Optionally, in step E, the temperature of the incubation is 130 ℃ to 200 ℃.
In some embodiments of the invention, in step E, the temperature of the incubation is typically, but not limited to, 130 ℃, 170 ℃ or 200 ℃.
Preferably, in the step E, the heat preservation time is 12h-24 h.
Alternatively, in step E, the acid water bath treatment is performed using an HCI solution.
The acid water bath treatment is to dissolve alpha-Ni (OH) 2 And (5) template.
Preferably, the concentration of the HCI solution is between 0.5M and 2M.
Preferably, the time of the acid water bath treatment is 0.5h-2 h.
The third aspect of the invention provides the application of the C/G/CNT-S negative electrode material in a lithium ion battery.
The C/G/CNT-S negative electrode material provided by the invention contributes to extremely high volume specific capacity for the lithium ion battery, so that the volume energy density of the lithium ion battery is greatly improved, and the lithium ion battery becomes smaller. And the obtained lithium ion battery has high reversible specific capacity and good capacity retention rate, and is suitable for large-scale popularization and use.
Some embodiments of the present invention will be described in detail below with reference to examples. The embodiments described below and the features of the embodiments can be combined with each other without conflict.
Example 1
The embodiment provides a C/G/CNT-S negative electrode material, which comprises the following specific steps:
1) selecting 5-micron carbon fiber cloth as a load substrate, and as shown in fig. 1, firstly, preprocessing the carbon fiber cloth: the carbon fiber cloth is immersed in a nitric acid solution for pretreatment for 1h at the temperature of 80 ℃, and then is washed with deionized water for multiple times until the pH value is neutral.
2) Selecting soluble salt of transition metal as Ni (NO) 3 ) 2 ·6H 2 O, catalytic growth source is Fe (NO) 3 ) 3 ·9H 2 O, 5-sulfosalicylic acid as chelating agent and urea as pH regulator.
3) And (4) according to molar ratio: 0.8 to 500ml of deionized water containing 20% by mass of urea was added Ni (NO) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 Adding 4.8mol of 5-sulfosalicylic acid dihydrate into the O powder, and stirring and dissolving the solute at 50 ℃ by using magnetic stirring.
4) Cutting a proper amount of the carbon fiber cloth obtained in the step 1) and placing the carbon fiber cloth at the bottom of a polytetrafluoroethylene lining, pouring the solution obtained in the step 3) into the polytetrafluoroethylene lining, transferring the polytetrafluoroethylene lining to a reaction kettle, reacting for 15 hours at 100 ℃, washing the polytetrafluoroethylene lining for multiple times by using deionized water and ethanol after the reaction is finished, and drying the polytetrafluoroethylene lining in an oven at 80 ℃ to obtain the G @ FeNi-LDHs material, wherein the material is shown in figure 2.
5) Transferring the G @ FeNi-LDHs obtained in the step 4) into a single-temperature-zone tube furnace, heating to the growth temperature of 980 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, and introducing 300ml/min of C after the temperature is stable 2 H 4 And (3) growing the carbon source gas for 10min, closing and heating after the reaction is finished, and naturally cooling the carbon source gas to room temperature in an inert atmosphere to obtain the C/G @ FeNi-LDHs material, wherein the material is shown in figure 3.
6) Treating the C/G @ FeNi-LDHs material with a 1M HCI solution at 80 ℃ for 2h and a 5M NaOH solution in a water bath for 1h, then transferring the material to an oven at 80 ℃ for drying, and then placing the obtained sample in CO at a volume ratio of 1:4 2 /N 2 Heat treating at 800 deg.C for 30min under atmosphere, water-bathing in 1M HCI solution for 1 hr, washing with deionized water, and oven dryingAnd drying to obtain a purified C/G/CNT sample. FIG. 4 is a sample of C-G-CNT left on a carbon fiber substrate after etching, with some degree of collapse due to loss of LDHs template support.
7) And uniformly spraying sulfur powder on the surface of the C/G/CNT sample, preserving the heat for 20 hours at 160 ℃ in an inert atmosphere, and naturally cooling to room temperature to obtain the C/G/CNT-S negative electrode sample.
Example 2
This example provides a C/G/CNT-S negative electrode material, which is different from example 1 in that the pH regulator is NaOH, and the rest of the raw materials and steps are the same as those in example 1, and are not repeated herein.
As can be seen from a scanning electron microscope, the growing LDHs are aggregated and precipitated into flower-shaped secondary particles by nano sheets with the sheet diameter of about 200-500nm, which is attributable to that when NaOH is used for assisting growth, the LDHs have large nucleation quantity and high nucleation speed, and the LDHs with large sheet diameter are difficult to obtain.
Example 3
This example provides a C/G/CNT-S negative electrode material, which is different from example 1 in that the pH regulator is ammonia water, and other raw materials and steps are the same as those in example 1, and are not described herein again.
As can be seen from a scanning electron microscope, the growing LDHs are gathered and precipitated on the surface of the carbon fiber cloth by nanosheets with the plate diameter of about 0.8-1 mu m, and a key factor influencing the size of the LDHs plate and controlling the growth speed of the LDHs template due to the adjustment of the pH value of the solution can be obviously found in comparative example 1 and example 2.
Example 4
The present embodiment provides a C/G/CNT-S negative electrode material, which is different from embodiment 1 in that, in step 1), carbon fiber cloth does not need to be pretreated with nitric acid, and is simply cleaned with absolute ethyl alcohol, and the remaining raw materials and steps are the same as those in embodiment 1, and are not described herein again.
As can be seen from a scanning electron microscope, the LDHs has low loading density on the surface of the carbon fiber cloth, and a local vacuum zone exists on the surface of the carbon fiber cloth, which can be attributed to the fact that the carbon fiber cloth can be activated by nitric acid pretreatment, so that the loading capacity is enhanced, and the nucleation growth of the LDHs on the surface of the carbon fiber cloth is facilitated.
Example 5
This example provides a C/G/CNT-S negative electrode material, different from example 1 in that, in step 3), Ni (NO) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 The molar ratio of the O powder to the sulfosalicylic acid dihydrate was 4:0.2 mol, and the other raw materials and steps were the same as in example 1 and will not be described again.
Example 6
This example provides a C/G/CNT-S negative electrode material, different from example 1 in that, in step 3), Ni (NO) 3 ) 2 ·6H 2 O and Fe (NO) 3 ) 3 ·9H 2 The molar ratio of O powder is 4:1.5, the sulfosalicylic acid dihydrate is 5.5mol, and the rest raw materials and steps are the same as those in example 1 and are not repeated.
Example 7
This example provides a C/G/CNT-S negative electrode material, different from example 1, in step 2), the soluble salt of the transition metal is CuSO 4 The rest of the raw materials and steps are the same as those in example 1, and are not described again here.
The result shows that the carbon dissolving capacity of Cu is very weak, copper is used as a growth catalytic source, the growth speed of graphene is slow, the number of layers is mostly single, and the construction of a stable graphene 'box' is not facilitated.
Comparative example 1
The comparative example provides a common graphene/sulfur composite negative electrode, which has a simple structure of compounding graphene with sulfur, and the preparation process is the same as the sulfur doping process of example 1, wherein the graphene used is purchased from element six in changzhou.
Comparative example 2
This comparative example provides a C/G/CNT-S anode material, different from example 1, in that the catalytic growth source is Co (NO) 3 ) 2 ·6H 2 O, the remaining raw materials and steps are the same as those in example 1 and are not described herein again.
As can be seen from a scanning electron microscope, only graphene grows on the surface of LDHs, and the 3D conductive network built is not ideal because CNT grows transversely.
Comparative example 3
This comparative example provides a C/G/CNT-S negative electrode material, which is different from example 1 in that the growth temperature of step 5) is 900 deg.C, and the other steps are the same as example 1. The result shows that only a small amount of graphene crystal domains grow on the surface of the LDHs, and a coated closed graphene box does not grow.
Test example 1
The C/G/CNT-S negative electrode samples obtained in examples 1 to 7 and the ordinary graphene/sulfur composite negative electrode provided in comparative example 1 were directly cut into a disc (disc diameter 12mm) as a negative electrode, and assembled into a button-type half cell to perform 0.5C charge and discharge test and 1C cycle 100-week capacity retention test, and the data obtained by the test are shown in table 1 below.
TABLE 1 Charge-discharge test results
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The C/G/CNT-S negative electrode material is characterized by comprising carbon fibers, a sulfur core, a graphene box and carbon nanotubes;
the graphene box arrays are arranged on the surface of the carbon fiber;
the sulfur core is located inside the graphene box;
the carbon nano tube is positioned on the surface of the graphene box and is bonded with the graphene box in a C-C bonding mode.
2. The method for preparing the C/G/CNT-S negative electrode material of claim 1, comprising the steps of:
step A: uniformly mixing soluble salt of transition metal, a catalytic growth source, a chelating agent and a pH value regulator to obtain a first solution;
and B: pouring the first solution into a container with carbon fiber cloth, transferring the container to a reaction kettle for reaction to obtain a G @ metal compound;
and C: transferring the G @ metal compound to a single-temperature-zone tube furnace, heating in a protective gas atmosphere, and introducing a carbon source gas to grow graphene to obtain a C/G @ metal compound;
step D: respectively carrying out acid-base treatment on the C/G @ metal compound, drying, and then carrying out CO treatment 2 And N 2 Carrying out heat treatment in mixed atmosphere, acid water bath treatment, washing and secondary drying to obtain C/G/CNT;
step E: and uniformly scattering sulfur powder on the surface of the C/G/CNT, and preserving heat in an inert atmosphere to obtain the C/G/CNT-S negative electrode material.
3. The method of claim 2, wherein the soluble salt of the transition metal comprises a soluble salt of nickel;
preferably, the soluble salt of nickel comprises at least one of nickel nitrate, nickel chloride and nickel sulfate;
preferably, the catalytic growth source comprises ferric nitrate;
preferably, the chelating agent comprises 5-sulfosalicylic acid;
preferably, the pH adjuster comprises at least one of urea, sodium hydroxide, and ammonia.
4. The method according to claim 2, wherein the molar ratio of the soluble salt of the transition metal, the catalytic growth source and the pH regulator is 4: (0.2-1.5): (0.8-4.5);
preferably, the chelating agent is added in an amount of the sum of the moles of the soluble salt of the transition metal and the catalytic growth source.
5. The preparation method according to claim 2, wherein in the step B, the reaction temperature is 80-150 ℃;
preferably, in the step B, the reaction time is 4-24 h;
preferably, the step B further comprises washing after the reaction and drying again to obtain a metal compound;
preferably, the temperature of the secondary drying is 60-100 ℃.
6. The method according to claim 2, wherein in step C, the rate of temperature increase is 2 ℃/min to 5 ℃/min;
preferably, the temperature after the temperature rise is 900-1100 ℃;
preferably, the carbon source gas comprises ethylene;
preferably, the carbon source gas is introduced at a rate of 200ml/min to 500 ml/min;
preferably, the time for growing the graphene is 10min to 30 min.
7. The method for preparing the alloy material according to claim 2, wherein the temperature of the heat treatment in the step D is 700-900 ℃;
preferably, the time of the heat treatment is 0.2h to 1 h.
8. The preparation method according to claim 2, wherein in the step E, the temperature of the heat preservation is 130-200 ℃;
preferably, in the step E, the heat preservation time is 12h-24 h.
9. The production method according to claim 2, characterized in that, in step E, the acid water bath treatment is performed using an HCI solution;
preferably, the concentration of the HCI solution is 0.5M-2M;
preferably, the time of the acid water bath treatment is 0.5h-2 h.
10. Use of the C/G/CNT-S negative electrode material of claim 1 or the C/G/CNT-S negative electrode material prepared by the preparation method of any one of claims 2 to 9 in a lithium ion battery.
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