CN111554934B - Biochar-loaded titanium dioxide for lithium-sulfur battery electrode and preparation method thereof - Google Patents

Biochar-loaded titanium dioxide for lithium-sulfur battery electrode and preparation method thereof Download PDF

Info

Publication number
CN111554934B
CN111554934B CN202010406206.XA CN202010406206A CN111554934B CN 111554934 B CN111554934 B CN 111554934B CN 202010406206 A CN202010406206 A CN 202010406206A CN 111554934 B CN111554934 B CN 111554934B
Authority
CN
China
Prior art keywords
biochar
titanium dioxide
lithium
sample
sulfur battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202010406206.XA
Other languages
Chinese (zh)
Other versions
CN111554934A (en
Inventor
黄剑锋
王海
王彩薇
田静
曹丽云
李嘉胤
郎蓉
钱程
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN202010406206.XA priority Critical patent/CN111554934B/en
Publication of CN111554934A publication Critical patent/CN111554934A/en
Application granted granted Critical
Publication of CN111554934B publication Critical patent/CN111554934B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/028—Positive electrodes
    • 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 biochar loaded titanium dioxide for a lithium-sulfur battery electrode and a preparation method thereof, wherein the preparation method comprises the following specific steps: (1) carbonizing the dandelion to obtain a carbonized product, namely biochar; (2) regulating and controlling the proportioning relation of the biochar and the surfactant, and preparing a surfactant solution; (3) preparing titanium dioxide in a surfactant solution to ensure that the titanium dioxide is fully adsorbed on the surface of the biochar; (4) growing titanium dioxide on the surface of the biochar in a high-temperature environment to obtain TiO2A structure of/C; (5) taking sulfur powder and TiO2Mixing the structure of/C to adsorb sulfur to TiO2Structure of/C. The preparation method provided by the invention is low in production cost and easy for industrial production, the prepared biomass carbon-loaded titanium dioxide for the lithium-sulfur battery electrode has strong adsorption capacity to sulfur, lithium polysulfide is not easy to dissolve in an electrolyte when the biomass carbon-loaded titanium dioxide is used for the lithium-sulfur battery, the electrochemical performance is excellent, and the capacity of the lithium-sulfur battery can be improved.

Description

Biochar-loaded titanium dioxide for lithium-sulfur battery electrode and preparation method thereof
Technical Field
The invention relates to the technical field of novel batteries, in particular to biochar-loaded titanium dioxide for a lithium-sulfur battery electrode and a preparation method thereof.
Background
The lithium ion battery is widely applied to daily life as a secondary battery, but with the progress of science and technology, the current mainstream lithium ion battery with lower energy density (200-300 Wh/kg) can not meet the requirements of people. Therefore, researchers are continuously pushing the energy density of lithium batteries to a higher level, and the energy density of the existing lithium ion battery systems depends on the specific capacity of the cathode material to a great extent.
Compared with the mainstream lithium ion battery anode material in the market, the sulfur electrode has high theoretical specific capacity which can reach 1675mAh/g, and the metal lithium has extremely high theoretical capacity (3861mAh/g) as the battery cathode, and meanwhile, the lithium sulfur battery works based on an electrochemical two-electron reaction system, the theoretical specific energy of the lithium sulfur battery is about 2600Wh/kg, and can reach more than 5 times of the capacity of the current mainstream battery product. In addition, the sulfur element has various advantages, such as abundant reserves, easy acquisition, capability of reducing the manufacturing cost of the battery, environmental friendliness and the like. Therefore, lithium-sulfur batteries are becoming a hot spot for the current development of batteries.
The biochar can be used as a carbon substrate of sulfur and widely applied to lithium-sulfur batteries, is an environment-friendly material, accords with the concept of sustainable development of the current society, has a natural pore structure, and has the advantage of high sulfur-carrying rate of the obtained biochar material, but has weak fastness to sulfur adsorption, and lithium polysulfide is easily dissolved in electrolyte after repeated charging and discharging, so that the development of a novel sulfur carrier based on biochar is still a potential challenge.
Titanium dioxide (TiO)2) The lithium ion battery cathode material has the advantages of low acquisition cost, abundant resources, environmental friendliness, extremely stable chemical properties, special energy band structure and intrinsic defects, and excellent conductivity, and can be applied to the lithium ion battery cathode material, and researchers have conducted extensive research on the lithium ion battery cathode material. Titanium dioxide is a meta-acidic amphoteric oxide, hardly reacts with other substances at normal temperature, and in a lithium-sulfur battery, different crystal structures of titanium dioxide show different adsorption capacities for sulfur.
Therefore, the crystal structure of the titanium dioxide is fully researched, the structure of the titanium dioxide is controlled by adopting an effective synthesis process, the aim of effectively improving the actual sulfur carrying amount of the composite powder can be achieved, the electrochemical performance is further improved, and the actual capacity of the battery is improved.
Disclosure of Invention
The invention aims to provide biomass carbon-supported titanium dioxide for a lithium-sulfur battery electrode, which has strong sulfur adsorption capacity and excellent electrochemical performance, and a preparation method thereof.
The purpose of the invention is realized by the following technical scheme:
a preparation method of biochar loaded titanium dioxide for a lithium-sulfur battery electrode comprises the following specific steps:
step (1), carbonizing 2g of dandelion to obtain a biological carbon skeleton precursor, and recording the precursor as a sample A;
step (2), preparing a surfactant solution: according to the mass ratio of the sample A to the surfactant hexadecylamine of 1: (1-5) taking a surfactant hexadecylamine, pouring the surfactant hexadecylamine into a container filled with 10mL of absolute ethyl alcohol, stirring until the surfactant hexadecylamine is completely dissolved, and marking the obtained solution as a solution B;
step (3), taking titanium isopropoxide and dropwise adding the titanium isopropoxide into the solution B to hydrolyze according to the volume ratio of 20 (1-1.5) of the absolute ethyl alcohol to the titanium isopropoxide in the step (2), dropwise adding ammonia water into the solution according to the volume ratio of 2:1 of the titanium isopropoxide to the ammonia water, and marking the obtained solution as a solution C;
adding the sample A into the solution C, stirring to enable titanium dioxide to be adsorbed on the surface of biochar, then carrying out centrifugal operation on the biochar, setting the centrifugal rotation speed to be 5000-8000 r/min, carrying out alcohol washing after the centrifugal operation is finished, finally placing the biochar in a vacuum drying box at the temperature of 80-100 ℃ for drying, collecting the dried sample and marking the dried sample as a sample D;
step (5), paving the sample D in a porcelain boat, putting the porcelain boat into a quartz tube protected by hydrogen-argon mixed gas, heating the porcelain boat from room temperature to 400-800 ℃ at a heating rate of 5-10 ℃/min, and then carrying out heat preservation to enable titanium dioxide to grow on the surface of the biochar to obtain a sample E;
and (6) sampling the sample E and the sulfur powder according to the mass ratio of 4:6, placing the sample E and the sulfur powder into a mortar, grinding until the two are uniformly mixed, then scattering the obtained mixture into a porcelain boat, placing the porcelain boat into a quartz tube filled with argon, raising the temperature to 155 ℃ at the heating rate of 5-8 ℃/min, preserving the temperature, and obtaining the biochar-loaded titanium dioxide for the lithium-sulfur battery electrode after the heat preservation is finished.
Further, before the dandelion is taken in the step (1), the dandelion is cleaned.
Further, the carbonization treatment in the step (1) comprises the following specific steps: putting 2g of dandelion into a porcelain boat, placing the porcelain boat in a tubular atmosphere furnace in an argon atmosphere, raising the temperature to 1000 ℃ at the heating rate of 5-10 ℃/min, then lowering the temperature to 300 ℃ at the cooling rate of 5-10 ℃/min, cooling the porcelain boat to room temperature to obtain a carbonized product, pickling and filtering the carbonized product, and then drying the carbonized product at the temperature of 60-80 ℃.
Further, the drying time in the step (1) is 15-30 h.
Further, the ammonia water extraction in the step (3) is carried out in a fume hood.
Further, the stirring time in the step (4) is 12-24 hours, and the drying time is 12-24 hours.
Further, the heat preservation time in the step (5) is 2 hours.
Further, the heat preservation time in the step (6) is 12 hours.
Further, the stirring is to place the container on a magnetic stirrer for stirring.
The biochar-supported titanium dioxide for the lithium-sulfur battery electrode prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the invention uses the biological carbon as the base to load the titanium dioxide, and regulates the structure of the titanium dioxide by regulating the proportion of the biological carbon and the surfactant to obtain the titanium dioxide with the characteristic of strong sulfur adsorption and the titanium dioxide with the characteristic of strong sulfur adsorptionTiO formed by titanium oxide and biochar with strong conductivity2the/C sulfur-carrying structure has a good ion transmission channel, the surface of the biological carbon is fully activated, and the biological carbon has strong adsorption capacity on titanium dioxide, so that sulfur is firmly adsorbed and combined on the structure of the biological carbon through the titanium dioxide; meanwhile, the preparation method provided by the invention has the advantages of abundant raw material resources, low production cost and easiness in industrial production.
The biomass carbon-loaded titanium dioxide for the lithium-sulfur battery electrode prepared by the preparation method has strong adsorption capacity on sulfur, and lithium polysulfide is not easy to dissolve in electrolyte when the biomass carbon-loaded titanium dioxide is applied to the lithium-sulfur battery; the electrochemical performance is excellent, and the capacity of the lithium-sulfur battery can be improved.
Drawings
FIG. 1 is an XRD (X-ray diffraction) diagram of sulfur adsorbed by biochar-supported titanium dioxide for a lithium sulfur battery electrode prepared by the preparation method of the invention;
fig. 2a, 2b and 2c are SEM images of biochar-supported titanium dioxide for lithium-sulfur battery electrodes prepared in example 1, example 2 and example 3, respectively, according to the present invention;
fig. 3a and 3b are performance graphs of biochar-supported titanium dioxide for lithium-sulfur battery electrodes prepared by the preparation method of the invention.
Detailed Description
The invention is described in further detail below with reference to the figures and specific embodiments.
Example 1:
weighing 2g of cleaned dandelion, putting the dandelion into a porcelain boat, heating the dandelion to 1000 ℃ at a heating rate of 10 ℃/min in a tubular atmosphere furnace in an argon atmosphere, then cooling the dandelion to 300 ℃ at a cooling rate of 10 ℃/min, cooling the dandelion to room temperature to obtain a carbonized product, carrying out acid cleaning and suction filtration on the carbonized product, and then drying the carbonized product for 15 hours at 80 ℃ to obtain a biological carbon skeleton precursor, namely biological carbon, which is marked as a sample A;
step (2), preparing a surfactant solution: according to the mass ratio of the sample A to the surfactant hexadecylamine of 1:1, taking a surfactant hexadecylamine, pouring the surfactant hexadecylamine into a container filled with 10mL of absolute ethyl alcohol, placing the container on a magnetic stirrer, stirring until the surfactant hexadecylamine is completely dissolved, and marking the obtained solution as a solution B;
step (3), sucking 0.5mL of titanium isopropoxide by using a liquid transfer gun and slowly dropwise adding the titanium isopropoxide into the solution B to hydrolyze the titanium isopropoxide according to the volume ratio of the anhydrous ethanol to the titanium isopropoxide in the step (2) of 20:1, sucking 0.25mL of ammonia water by using the liquid transfer gun in a fume hood according to the volume ratio of the titanium isopropoxide to the ammonia water of 2:1, dropwise adding the ammonia water into the solution B with the titanium isopropoxide, and recording the obtained solution as a solution C;
adding the sample A into the solution C, stirring for 12 hours to enable titanium dioxide to be fully adsorbed on the surface of the biochar, then carrying out centrifugal operation on the biochar, setting the centrifugal rotation speed to be 5000r/min, carrying out alcohol washing after the centrifugal operation is finished, finally placing the biochar in a vacuum drying oven at the temperature of 80 ℃ for drying for 24 hours, collecting the dried sample and marking the dried sample as a sample D;
step (5), paving the sample D in a porcelain boat, putting the porcelain boat into a quartz tube protected by hydrogen-argon mixed gas, heating the porcelain boat from room temperature to 400 ℃ at the heating rate of 5 ℃/min, and then preserving heat for 2 hours after the heating is finished, so that titanium dioxide grows on the surface of biochar to obtain a sample E;
and (6) sampling 0.16 g of sample E and 0.24g of sulfur powder according to the mass ratio of 4:6, fully grinding the samples in a mortar, after grinding the samples until the samples and the sulfur powder are uniformly mixed, scattering the obtained mixture into a porcelain boat, putting the porcelain boat into a quartz tube filled with argon, raising the temperature to 155 ℃ at the heating rate of 5 ℃/min, preserving the temperature for 12 hours, and obtaining the biochar-loaded titanium dioxide for the lithium-sulfur battery electrode after the heat preservation is finished.
Example 2:
weighing 2g of cleaned dandelion, putting the dandelion into a porcelain boat, heating the dandelion to 1000 ℃ at a heating rate of 5 ℃/min in a tubular atmosphere furnace in an argon atmosphere, then cooling the dandelion to 300 ℃ at a cooling rate of 10 ℃/min, cooling the dandelion to room temperature to obtain a carbonized product, carrying out acid cleaning and suction filtration on the carbonized product, and then drying the carbonized product for 20 hours at 80 ℃ to obtain a biological carbon skeleton precursor, namely biological carbon, which is marked as a sample A;
step (2), preparing a surfactant solution: according to the mass ratio of the sample A to the surfactant hexadecylamine of 1: taking a surfactant hexadecylamine, pouring the surfactant hexadecylamine into a container filled with 10mL of absolute ethyl alcohol, placing the container on a magnetic stirrer, stirring until the surfactant hexadecylamine is completely dissolved, and marking the obtained solution as a solution B;
step (3), sucking 0.65mL of titanium isopropoxide by using a liquid-transferring gun and slowly dropwise adding the titanium isopropoxide into the solution B to hydrolyze the titanium isopropoxide according to the volume ratio of the anhydrous ethanol to the titanium isopropoxide in the step (2) being 20:1.3, sucking 0.32mL of ammonia water by using the liquid-transferring gun in a fume hood according to the volume ratio of the titanium isopropoxide to the ammonia water being 2:1, dropwise adding the ammonia water into the solution B with the titanium isopropoxide, and marking the obtained solution as a solution C;
adding the sample A into the solution C, stirring for 18h to enable titanium dioxide to be fully adsorbed on the surface of the biochar, then carrying out centrifugal operation on the biochar, setting the centrifugal rotation speed to be 6500r/min, carrying out alcohol washing after the centrifugal operation is finished, finally placing the biochar in a vacuum drying oven at the temperature of 90 ℃ for drying for 18h, collecting the dried sample and marking the dried sample as a sample D;
step (5), paving the sample D in a porcelain boat, putting the porcelain boat into a quartz tube protected by hydrogen-argon mixed gas, heating the porcelain boat from room temperature to 600 ℃ at the heating rate of 8 ℃/min, and then preserving heat for 2 hours after the heating is finished, so that titanium dioxide grows on the surface of biochar to obtain a sample E;
and (6) sampling 0.16 g of sample E and 0.24g of sulfur powder according to the mass ratio of 4:6, fully grinding the samples in a mortar, after grinding the samples until the samples and the sulfur powder are uniformly mixed, scattering the obtained mixture into a porcelain boat, putting the porcelain boat into a quartz tube filled with argon, raising the temperature to 155 ℃ at the heating rate of 6 ℃/min, preserving the temperature for 12 hours, and obtaining the biochar-loaded titanium dioxide for the lithium-sulfur battery electrode after the heat preservation is finished.
Example 3:
weighing 2g of cleaned dandelion, putting the dandelion into a porcelain boat, heating the dandelion to 1000 ℃ at a heating rate of 8 ℃/min in a tubular atmosphere furnace in an argon atmosphere, cooling the dandelion to 300 ℃ at a cooling rate of 5 ℃/min, cooling the dandelion to room temperature to obtain a carbonized product, carrying out acid cleaning and suction filtration on the carbonized product, and then drying the carbonized product for 30 hours at the temperature of 60 ℃ to obtain a biological carbon skeleton precursor, namely biological carbon, which is marked as a sample A;
step (2), preparing a surfactant solution: according to the mass ratio of the sample A to the surfactant hexadecylamine of 1:5, taking a surfactant hexadecylamine, pouring the surfactant hexadecylamine into a container filled with 10mL of absolute ethyl alcohol, placing the container on a magnetic stirrer, stirring until the surfactant hexadecylamine is completely dissolved, and marking the obtained solution as a solution B;
step (3), sucking 0.75mL of titanium isopropoxide by using a liquid-transferring gun and slowly dropwise adding the sucked 0.38mL of ammonia water into the solution B dropwise according to the volume ratio of the titanium isopropoxide to the ammonia water of 2:1, and marking the obtained solution as a solution C, wherein the volume ratio of the absolute ethyl alcohol to the titanium isopropoxide in the step (2) is 20: 1.5;
adding the sample A into the solution C, stirring for 24 hours to enable titanium dioxide to be fully adsorbed on the surface of the biochar, then carrying out centrifugal operation on the biochar, setting the centrifugal rotation speed to be 8000r/min, carrying out alcohol washing after the centrifugal operation is finished, finally placing the biochar in a vacuum drying oven at the temperature of 100 ℃ for drying for 12 hours, collecting the dried sample and marking the dried sample as a sample D;
step (5), paving the sample D in a porcelain boat, putting the porcelain boat into a quartz tube protected by hydrogen-argon mixed gas, heating the porcelain boat from room temperature to 800 ℃ at the heating rate of 10 ℃/min, and then preserving heat for 2 hours after the heating is finished, so that titanium dioxide grows on the surface of biochar to obtain a sample E;
and (6) sampling 0.16 g of sample E and 0.24g of sulfur powder according to the mass ratio of 4:6, fully grinding the samples in a mortar, after grinding the samples until the samples and the sulfur powder are uniformly mixed, scattering the obtained mixture into a porcelain boat, putting the porcelain boat into a quartz tube filled with argon, raising the temperature to 155 ℃ at the heating rate of 8 ℃/min, preserving the temperature for 12 hours, and obtaining the biochar-loaded titanium dioxide for the lithium-sulfur battery electrode after the heat preservation is finished.
Example 4:
weighing 2g of cleaned dandelion, putting the dandelion into a porcelain boat, heating the dandelion to 1000 ℃ at a heating rate of 8 ℃/min in a tubular atmosphere furnace in an argon atmosphere, then cooling the dandelion to 300 ℃ at a cooling rate of 8 ℃/min, cooling the dandelion to room temperature to obtain a carbonized product, carrying out acid cleaning and suction filtration on the carbonized product, and then drying the carbonized product for 25 hours at 80 ℃ to obtain a biological carbon skeleton precursor, namely biological carbon, which is marked as a sample A;
step (2), preparing a surfactant solution: according to the mass ratio of the sample A to the surfactant hexadecylamine of 1:1, taking a surfactant hexadecylamine, pouring the surfactant hexadecylamine into a container filled with 10mL of absolute ethyl alcohol, placing the container on a magnetic stirrer, stirring until the surfactant hexadecylamine is completely dissolved, and marking the obtained solution as a solution B;
step (3), sucking 0.5mL of titanium isopropoxide by using a liquid transfer gun and slowly dropwise adding the titanium isopropoxide into the solution B to hydrolyze the titanium isopropoxide according to the volume ratio of the anhydrous ethanol to the titanium isopropoxide in the step (2) of 20:1, sucking 0.25mL of ammonia water by using the liquid transfer gun in a fume hood according to the volume ratio of the titanium isopropoxide to the ammonia water of 2:1, dropwise adding the ammonia water into the solution B with the titanium isopropoxide, and recording the obtained solution as a solution C;
adding the sample A into the solution C, stirring for 15h to enable titanium dioxide to be fully adsorbed on the surface of the biochar, then carrying out centrifugal operation on the biochar, setting the centrifugal rotation speed to be 5000r/min, carrying out alcohol washing after the centrifugal operation is finished, finally placing the biochar in a vacuum drying oven at the temperature of 80 ℃ for drying for 15h, collecting the dried sample and marking the dried sample as a sample D;
step (5), paving the sample D in a porcelain boat, putting the porcelain boat into a quartz tube protected by hydrogen-argon mixed gas, heating the porcelain boat from room temperature to 500 ℃ at the heating rate of 5 ℃/min, and then preserving heat for 2 hours after the heating is finished, so that titanium dioxide grows on the surface of biochar to obtain a sample E;
and (6) sampling 0.16 g of sample E and 0.24g of sulfur powder according to the mass ratio of 4:6, fully grinding the samples in a mortar, after grinding the samples until the samples and the sulfur powder are uniformly mixed, scattering the obtained mixture into a porcelain boat, putting the porcelain boat into a quartz tube filled with argon, raising the temperature to 155 ℃ at the heating rate of 7 ℃/min, preserving the temperature for 12 hours, and obtaining the biochar-loaded titanium dioxide for the lithium-sulfur battery electrode after the heat preservation is finished.
Example 5:
weighing 2g of cleaned dandelion, putting the dandelion into a porcelain boat, heating the dandelion to 1000 ℃ at a heating rate of 5 ℃/min in a tubular atmosphere furnace in an argon atmosphere, cooling the dandelion to 300 ℃ at a cooling rate of 5 ℃/min, cooling the dandelion to room temperature to obtain a carbonized product, carrying out acid cleaning and suction filtration on the carbonized product, and then drying the carbonized product for 18 hours at 80 ℃ to obtain a biological carbon skeleton precursor, namely biological carbon, which is marked as a sample A;
step (2), preparing a surfactant solution: according to the mass ratio of the sample A to the surfactant hexadecylamine of 1:1, taking a surfactant hexadecylamine, pouring the surfactant hexadecylamine into a container filled with 10mL of absolute ethyl alcohol, placing the container on a magnetic stirrer, stirring until the surfactant hexadecylamine is completely dissolved, and marking the obtained solution as a solution B;
step (3), sucking 0.5mL of titanium isopropoxide by using a liquid transfer gun and slowly dropwise adding the titanium isopropoxide into the solution B to hydrolyze the titanium isopropoxide according to the volume ratio of the anhydrous ethanol to the titanium isopropoxide in the step (2) of 20:1, sucking 0.25mL of ammonia water by using the liquid transfer gun in a fume hood according to the volume ratio of the titanium isopropoxide to the ammonia water of 2:1, dropwise adding the ammonia water into the solution B with the titanium isopropoxide, and recording the obtained solution as a solution C;
adding the sample A into the solution C, stirring for 15h to enable titanium dioxide to be fully adsorbed on the surface of the biochar, then carrying out centrifugal operation on the biochar, setting the centrifugal rotation speed to be 5000r/min, carrying out alcohol washing after the centrifugal operation is finished, finally placing the biochar in a vacuum drying oven at the temperature of 85 ℃ for drying for 22h, collecting the dried sample and marking the dried sample as a sample D;
step (5), paving the sample D in a porcelain boat, putting the porcelain boat into a quartz tube protected by hydrogen-argon mixed gas, heating the porcelain boat from room temperature to 500 ℃ at the heating rate of 7 ℃/min, and then preserving heat for 2 hours after the heating is finished, so that titanium dioxide grows on the surface of biochar to obtain a sample E;
and (6) sampling 0.16 g of sample E and 0.24g of sulfur powder according to the mass ratio of 4:6, fully grinding the samples in a mortar, after grinding the samples until the samples and the sulfur powder are uniformly mixed, scattering the obtained mixture into a porcelain boat, putting the porcelain boat into a quartz tube filled with argon, raising the temperature to 155 ℃ at the heating rate of 6 ℃/min, preserving the temperature for 12 hours, and obtaining the biochar-loaded titanium dioxide for the lithium-sulfur battery electrode after the heat preservation is finished.
The results shown in fig. 1, fig. 2a, fig. 2b, fig. 2c, fig. 3a, and fig. 3b were obtained by analyzing and characterizing the biochar-supported titanium dioxide for lithium sulfur battery electrodes prepared in example 1, example 2, and example 3.
In FIG. 1, the ratios of 1:1, 1:3 and 1:5 of the biochar and the surfactant are respectively 1:1, 1:3 and 1:5, and it can be seen from FIG. 1 that the biochar-supported titanium dioxide for the lithium-sulfur battery electrode prepared by the invention successfully adsorbs and firmly bonds sulfur elements on the substrate.
As can be seen from fig. 2a, 2b and 2c, the biochar-supported titanium dioxide substrate for the lithium-sulfur battery electrode prepared by the invention has a large number of substances participating in the electrochemical reaction on the surface, and as can be seen from comparing fig. 2a, 2b and 2c, when the proportion of the biochar and the surfactant is 1:1, the substances participating in the electrochemical reaction on the surface of the substrate are the most, and further, when the proportion of the biochar and the surfactant is 1:1, the structure of the obtained titanium dioxide has a more beneficial effect on the performance, and the electrochemical performance can be improved.
From fig. 3a and fig. 3b, it can be seen that the biochar-loaded titanium dioxide for the lithium-sulfur battery electrode prepared by the invention has high first-cycle discharge capacity and can be used for long cycle in practical application, when the proportion of the biochar and the surfactant is 1:1, as shown in fig. 3a, the first-cycle discharge capacity is 798mAh/g, after long cycle, the capacity can be maintained at 237mAh/g, and as shown in fig. 3b, the reversible capacity can be maintained at 284 mAh/g.
Therefore, when the biochar-loaded titanium dioxide for the lithium-sulfur battery electrode prepared by the invention is actually applied to the lithium-sulfur battery, the electrochemical performance of the biochar-loaded titanium dioxide is obviously superior to that of the conventional mainstream lithium battery and lithium-sulfur battery.

Claims (9)

1. A preparation method of biochar loaded titanium dioxide for a lithium-sulfur battery electrode is characterized by comprising the following specific steps:
step (1), carbonizing 2g of dandelion to obtain a biological carbon skeleton precursor, and recording the precursor as a sample A; the carbonization treatment comprises the following specific steps: putting 2g of dandelion into a porcelain boat, placing the porcelain boat in a tubular atmosphere furnace in an argon atmosphere, heating to 1000 ℃ at a heating rate of 5-10 ℃/min, then cooling to 300 ℃ at a cooling rate of 5-10 ℃/min, cooling to room temperature to obtain a carbonized product, carrying out acid washing and suction filtration on the carbonized product, and then drying at 60-80 ℃;
step (2), preparing a surfactant solution: according to the mass ratio of the sample A to the surfactant hexadecylamine of 1: (1-5) taking a surfactant hexadecylamine, pouring the surfactant hexadecylamine into a container filled with 10mL of absolute ethyl alcohol, stirring until the surfactant hexadecylamine is completely dissolved, and marking the obtained solution as a solution B;
step (3), taking titanium isopropoxide and dropwise adding the titanium isopropoxide into the solution B to hydrolyze according to the volume ratio of 20 (1-1.5) of the absolute ethyl alcohol to the titanium isopropoxide in the step (2), dropwise adding ammonia water into the solution according to the volume ratio of 2:1 of the titanium isopropoxide to the ammonia water, and marking the obtained solution as a solution C;
adding the sample A into the solution C, stirring to enable titanium dioxide to be adsorbed on the surface of the biochar, then carrying out centrifugal operation on the biochar, setting the centrifugal rotation speed to be 5000-8000 r/min, carrying out alcohol washing after the centrifugal operation is finished, finally placing the biochar in a vacuum drying oven at the temperature of 80-100 ℃ for drying, collecting the dried sample and marking the dried sample as a sample D;
step (5), paving the sample D in a porcelain boat, putting the porcelain boat into a quartz tube protected by hydrogen-argon mixed gas, heating the porcelain boat from room temperature to 400-800 ℃ at a heating rate of 5-10 ℃/min, and then carrying out heat preservation to enable titanium dioxide to grow on the surface of the biochar to obtain a sample E;
and (6) sampling the sample E and the sulfur powder according to the mass ratio of 4:6, placing the sample E and the sulfur powder into a mortar, grinding until the two are uniformly mixed, then scattering the obtained mixture into a porcelain boat, placing the porcelain boat into a quartz tube filled with argon, raising the temperature to 155 ℃ at the heating rate of 5-8 ℃/min, preserving the temperature, and obtaining the biochar-loaded titanium dioxide for the lithium-sulfur battery electrode after the heat preservation is finished.
2. The method of preparing biochar-supported titanium dioxide for a lithium sulfur battery electrode according to claim 1, wherein: and (2) cleaning the dandelion before the dandelion is taken in the step (1).
3. The method of preparing biochar-supported titanium dioxide for a lithium sulfur battery electrode according to claim 1, wherein: the drying time in the step (1) is 15-30 h.
4. The method of preparing biochar-supported titanium dioxide for a lithium sulfur battery electrode according to claim 1, wherein: the ammonia water extraction operation in the step (3) is carried out in a fume hood.
5. The method of preparing biochar-supported titanium dioxide for a lithium sulfur battery electrode according to claim 1, wherein: the stirring time in the step (4) is 12-24 hours, and the drying time is 12-24 hours.
6. The method of preparing biochar-supported titanium dioxide for a lithium sulfur battery electrode according to claim 1, wherein: the heat preservation time in the step (5) is 2 hours.
7. The method of preparing biochar-supported titanium dioxide for a lithium sulfur battery electrode according to claim 1, wherein: the heat preservation time in the step (6) is 12 hours.
8. The method for preparing the biochar-supported titanium dioxide for the lithium-sulfur battery electrode according to any one of the above items, characterized by comprising the following steps: the stirring is to place the container on a magnetic stirrer for stirring.
9. The biochar-supported titanium dioxide for the lithium-sulfur battery electrode prepared by the preparation method.
CN202010406206.XA 2020-05-14 2020-05-14 Biochar-loaded titanium dioxide for lithium-sulfur battery electrode and preparation method thereof Active CN111554934B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202010406206.XA CN111554934B (en) 2020-05-14 2020-05-14 Biochar-loaded titanium dioxide for lithium-sulfur battery electrode and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202010406206.XA CN111554934B (en) 2020-05-14 2020-05-14 Biochar-loaded titanium dioxide for lithium-sulfur battery electrode and preparation method thereof

Publications (2)

Publication Number Publication Date
CN111554934A CN111554934A (en) 2020-08-18
CN111554934B true CN111554934B (en) 2021-09-07

Family

ID=72008231

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010406206.XA Active CN111554934B (en) 2020-05-14 2020-05-14 Biochar-loaded titanium dioxide for lithium-sulfur battery electrode and preparation method thereof

Country Status (1)

Country Link
CN (1) CN111554934B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113087014B (en) * 2021-03-31 2022-07-01 江西普瑞森新能源科技有限公司 Preparation method of carbon/selenium-doped titanium dioxide lithium-sulfur battery positive electrode material
CN113903912B (en) * 2021-09-30 2023-06-23 常熟理工学院 Preparation method of carbon-loaded titanium carbide material, and product and application obtained by preparation method

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104269559A (en) * 2014-10-10 2015-01-07 南京中储新能源有限公司 TiO2 coated sulfur/ordered mesoporous carbon composite cathode material and preparation method thereof
CN104362323A (en) * 2014-10-31 2015-02-18 天津大学 Method for quickly preparing lithium ion battery anode material by one-step solvent hot process
CN106129343A (en) * 2016-05-25 2016-11-16 福建翔丰华新能源材料有限公司 A kind of preparation method of Graphene titanium dioxide microballoon sphere
CN106549159A (en) * 2015-09-16 2017-03-29 中国科学院大连化学物理研究所 A kind of lithium-sulfur cell porous carbon materials and its preparation and application
CN108735979A (en) * 2017-04-24 2018-11-02 清华大学 The preparation method of negative electrode of lithium ion battery
CN109585827A (en) * 2018-11-28 2019-04-05 东莞理工学院 A kind of preparation method of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material
CN109574005A (en) * 2018-11-30 2019-04-05 陕西科技大学 A kind of preparation method of lithium-sulfur cell cathode biology carbon material
CN109698356A (en) * 2018-12-27 2019-04-30 中科廊坊过程工程研究院 A kind of positive electrode modifying agent and its preparation method and application

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103296240A (en) * 2013-05-28 2013-09-11 中科院广州化学有限公司 High-performance flexible composite nonwoven fabric membrane for lithium ion battery, as well as preparation method and application of membrane
CN105489896A (en) * 2015-11-24 2016-04-13 青岛能迅新能源科技有限公司 Active sulfur electrode paste adopting inorganic modified vegetable adhesive and preparation method of active sulfur electrode paste
US10950866B2 (en) * 2017-03-21 2021-03-16 Sparkle Power Llc Battery with active materials stored on or in carbon nanosheets
CN108767204A (en) * 2018-03-30 2018-11-06 合肥国轩高科动力能源有限公司 A kind of lithium-sulfur cell TiO2The preparation method of/C composite

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104269559A (en) * 2014-10-10 2015-01-07 南京中储新能源有限公司 TiO2 coated sulfur/ordered mesoporous carbon composite cathode material and preparation method thereof
CN104362323A (en) * 2014-10-31 2015-02-18 天津大学 Method for quickly preparing lithium ion battery anode material by one-step solvent hot process
CN106549159A (en) * 2015-09-16 2017-03-29 中国科学院大连化学物理研究所 A kind of lithium-sulfur cell porous carbon materials and its preparation and application
CN106129343A (en) * 2016-05-25 2016-11-16 福建翔丰华新能源材料有限公司 A kind of preparation method of Graphene titanium dioxide microballoon sphere
CN108735979A (en) * 2017-04-24 2018-11-02 清华大学 The preparation method of negative electrode of lithium ion battery
CN109585827A (en) * 2018-11-28 2019-04-05 东莞理工学院 A kind of preparation method of coated by titanium dioxide sulfur doping carbon nanotube lithium-sulphur cell positive electrode material
CN109574005A (en) * 2018-11-30 2019-04-05 陕西科技大学 A kind of preparation method of lithium-sulfur cell cathode biology carbon material
CN109698356A (en) * 2018-12-27 2019-04-30 中科廊坊过程工程研究院 A kind of positive electrode modifying agent and its preparation method and application

Also Published As

Publication number Publication date
CN111554934A (en) 2020-08-18

Similar Documents

Publication Publication Date Title
CN109678130A (en) A kind of hard carbon material for sodium-ion battery cathode and preparation method thereof and related sodium-ion battery
CN110212194B (en) Preparation method and application of one-dimensional MOF @ ZIF core-shell structure
CN107275587B (en) A kind of lithium ion silicon-carbon composite cathode material and preparation method thereof
CN111244448B (en) In-situ carbon-coated high-rate large-size Prussian blue type sodium ion positive electrode material and preparation method thereof
CN112349899B (en) Silicon-based composite negative electrode material, preparation method thereof and lithium ion battery
CN108258211B (en) Method for preparing titanium dioxide/graphene composite material by supercritical carbon dioxide fluid and application
CN105845911A (en) Method for preparing porous silicon carbon nanotube composite negative electrode material of lithium ion battery by diatomite
CN109755540B (en) Lithium-sulfur battery positive electrode material and preparation method thereof
CN111554934B (en) Biochar-loaded titanium dioxide for lithium-sulfur battery electrode and preparation method thereof
CN106252664B (en) The super loose carbonization structure porous carbon nanofiber of one kind and its electrostatic spinning-carbonization manufacture method
CN103730638A (en) Preparation method of nitrogen-doped carbon material
CN111439738B (en) Biomass hard carbon, lithium ion battery, preparation method and application thereof
CN110098396A (en) A kind of lithium-sulfur battery composite cathode material and preparation method thereof and battery
CN108987733B (en) Preparation method of active porous carbon @ FeS of lithium ion battery cathode material
CN111082050A (en) Lithium ion battery cathode material and preparation method thereof
CN105895871B (en) A kind of porous Si-C composite material and preparation method and application
CN109319757A (en) The method for preparing hollow open onion carbon lithium ion cell negative electrode material
CN110739429A (en) Preparation method of functional interlayer of lithium-sulfur battery
CN109728260A (en) The preparation method of the carbon-coated cementite combination electrode material of nitrogen sulfur doping
CN106920937B (en) Preparation method of electrode composite material
CN104167541B (en) For the positive electrode preparation technology of sodium-ion battery
CN107739031A (en) A kind of method that lithium ion carbon negative pole material is prepared with bacteria residue waste material
CN107732209B (en) Method for preparing lithium ion carbon negative electrode material from mixed bacteria residue waste
CN104701531B (en) In-situ carbon-coating hexagon K0.7[Fe0.5Mn0.5]O2 nano material as well as preparation method and application thereof
CN103346315A (en) Preparation method of carbon-coated lithium iron phosphate material with carbon black as carbon source

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant