CN107732203B - Preparation method of nano cerium dioxide/graphene/sulfur composite material - Google Patents
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Abstract
The invention relates to a preparation method of a nano cerium dioxide/graphene/sulfur composite material. The method comprises the following steps: adding a carbon disulfide/sulfur solution into the graphene oxide/nano cerium dioxide mixed suspension to obtain a graphene oxide/nano cerium dioxide/sulfur mixed solution, putting the mixed solution into a stainless steel reaction kettle, and carrying out hydrothermal reaction for 5-24h at the temperature of 100-; cleaning, and carrying out vacuum freeze drying to obtain a nano cerium dioxide/graphene/sulfur composite material; the method innovatively completes the graphene oxide reduction and the nano metal oxide doping with the loaded sulfur solvent thermal reaction in one step, improves the reaction efficiency, has a simple preparation process, and overcomes the defects of low utilization rate, poor rate performance, short cycle life, low reaction efficiency and complex preparation process of the positive active material of the lithium-sulfur battery in the prior art.
Description
Technical Field
The invention relates to the field of preparation of lithium-sulfur battery cathode materials, in particular to a preparation method and application of a nano cerium oxide/graphene/sulfur composite material.
Background
In recent years, with the decline of oil production and the increase of global environmental pollution, countries around the world generally recognize that the replacement of fuel oil vehicles by clean and pollution-free electric vehicles is a necessary choice for the continuous development of the country. The power battery technology with high specific capacity becomes the key of the development of pure electric vehicles. However, the specific energy of commercial lithium ion batteries based on lithium intercalation/deintercalation is limited by the theoretical specific capacity of the cathode material, and the specific energy of the current lithium ion batteries is difficult to exceed 200 Wh/kg. The positive electrode material has not been the bottleneck of limiting the specific capacity of the lithium ion battery, so that the development of a novel lithium battery positive electrode material with higher specific energy is urgently needed. The lithium-sulfur battery is a high-energy-density secondary battery with great development potential and application prospect. It has a high specific capacity (1675mAh/g) and a high energy density (2600 Wh/kg). In addition, sulfur as a positive electrode active material also exhibits incomparable advantages in terms of source, cost, environmental friendliness, and the like.
However, the current problems of low utilization rate of active materials, low cycle life, poor safety and the like exist, which seriously restrict the development of lithium-sulfur batteries. However, the current problems of low utilization rate of active materials, low cycle life, poor safety and the like exist, which seriously restrict the development of lithium-sulfur batteries. The main reasons for the above problems are as follows: (1) the insulating property of elemental sulfur. Elemental sulfur is an insulator of electrons and ions at room temperature and has an electron conductivity of 5X 10 at room temperature-30Scm-1Ion conductivity of 10-15Resulting in an increase in internal resistance of the lithium-sulfur battery and a low utilization rate of active materials. (2) Dissolution of polysulfide compound, intermediate polysulfide (Li) produced by electrochemical reaction2SnN > 4) dissolves in the electrolyte, diffuses to and reacts with the lithium negative electrode, causing a "shuttling effect". (3) Reaction end product Li2S is also an electronic insulator and can be deposited on the sulfur electrode, and lithium ions have low migration speed in solid lithium sulfide, so that the electrochemical reaction kinetic speed is reduced; (4) sulphur and end product Li2The density of S is different, and the volume expansion of sulfur after lithiation is about 79 percent, which is easy to cause Li2Pulverization of S causes safety problems of the lithium sulfur battery.
In order to solve the above problems, most studies have been made in recent years on a sulfur-carbon composite positive electrode material in which a conductive carbon material is used as a sulfur carrier and a conductive skeleton. The graphene has excellent conductivity, large specific surface area, strong chemical stability and mechanical property and a unique two-dimensional porous network geometric structure, can shorten an electron and ion transmission path in a lithium-sulfur battery, improves the electrochemical activity of elemental sulfur, and during charge and discharge cycles, a peripheral layered graphene structure can coat the generated soluble lithium polysulfide and limit the lithium polysulfide inside an electrode material, so that the shuttle effect can be slowed down, the coulombic efficiency is improved, the specific capacity of the electrode is improved, and the cycle life of the battery is prolonged. According to the report, various metal oxides are subjected to synthesis strategies and preparation methods such as hydrothermal, solvothermal, coprecipitation, atomic layer deposition and sol-gel to obtain metal oxide-graphene composites with different sizes such as nano-scale and micron-scale, different appearances such as granular, rod-like, porous, spherical, layered and flower-like metal oxides with different dimensions, and the modified graphene can be embedded, rolled and implanted in different modes to form layered structures, sandwich structures, hollow core-shell structures, mixed structures and other forms. The excellent structure enables the physical adsorption or chemical interaction between the composite material and polysulfide ions to better limit the dissolution of the polysulfide ions and avoid generating a shuttle effect, thereby playing a good role in fixing active substances (such as sulfur) and enabling the sulfur-based composite material to show better cycle stability.
Disclosure of Invention
The technical scheme adopted by the invention for solving the technical problem is as follows: the invention provides a preparation method of a nano cerium dioxide/graphene/sulfur composite material, aiming at the problems of low utilization rate of active substances of a lithium-sulfur battery positive electrode, poor rate capability and short cycle life. The method innovatively completes the graphene oxide reduction and the nano metal oxide doping with the loaded sulfur solvent thermal reaction in one step, improves the reaction efficiency, has a simple preparation process, and overcomes the defects of low utilization rate, poor rate performance, short cycle life, low reaction efficiency and complex preparation process of the positive active material of the lithium-sulfur battery in the prior art. Meanwhile, the nano cerium dioxide/graphene/sulfur composite material prepared by the method has excellent electrochemical performance as a lithium-sulfur battery anode material, and the initial discharge capacity of the material is up to 1400mAh/g under the multiplying power of 0.1C.
The technical scheme of the invention is as follows:
a preparation method of a nano cerium dioxide/graphene/sulfur composite material comprises the following steps:
the first step is as follows: dissolving nano sulfur powder in carbon disulfide to prepare 2-30mg/mL carbon disulfide/sulfur solution;
the second step is that: respectively adding graphene oxide and nano cerium dioxide into deionized water, and ultrasonically dispersing the solution for 1-3 hours at normal temperature by using an ultrasonic dispersion instrument to obtain a graphene oxide/nano cerium dioxide mixed suspension;
wherein, the mass ratio of graphene oxide: nano ceria is 1:1-20, the sum of the mass of graphene oxide and nano ceria: deionized water with the mass ratio of 0.001-0.03: 1;
the third step: adding the prepared carbon disulfide/sulfur solution into the graphene oxide/nano cerium dioxide mixed suspension, stirring for 1-3h at normal temperature to obtain a graphene oxide/nano cerium dioxide/sulfur mixed solution, putting the mixed solution into a stainless steel reaction kettle, and carrying out hydrothermal reaction for 5-24h at the temperature of 100 ℃ and 200 ℃; then washing the hydrogel obtained by the reaction for 2-6 times at 60-110 ℃ by using deionized water, and carrying out vacuum freeze drying on the obtained product for 5-12h at-45 ℃ to obtain the nano cerium dioxide/graphene/sulfur composite material;
wherein, the mass ratio of graphene oxide: 1:1-5 of sulfur.
The power of the ultrasonic disperser in the second step is 35-60 kHz.
The vacuum degree of vacuum drying in the third step is 20 Pa.
In the preparation method of the nano cerium oxide/graphene/sulfur composite material, the raw materials are commercially available, and the equipment and process are well known to those skilled in the art.
Compared with the prior art, the method has the prominent substantive characteristics as follows:
in the preparation method, the nano cerium dioxide is prepared by adopting a precipitation method, the process is simple, the production cost is low, the industrialization is easy to realize, and the nano particles with small particles and high purity can be prepared. The preparation process and material modification of the traditional graphene/sulfur composite material are improved by using the nano cerium dioxide, so that the problem of aggregation among graphene sheet layers is effectively avoided, the dissolution of polysulfide in electrolyte in the charge-discharge process is effectively inhibited, and the utilization rate of active sulfur and the charge-discharge electrochemical performance are improved.
The invention has the following beneficial results:
(1) the composite cathode material prepared by the invention adsorbs sulfur in the middle of the three-dimensional graphene grid containing the metal oxide, so that polysulfide formed in the battery circulation process can be effectively prevented from being dissolved in electrolyte, and the battery has good circulation stability.
(2) The positive electrode prepared from the positive electrode material provided by the invention is applied to a lithium-sulfur battery, and has the advantages of high capacity, good cycle performance, wide raw material source, low cost, greenness, no pollution and the like. The nano cerium dioxide has an adsorption effect on polysulfide in the charge-discharge process, so that the dissolution of the polysulfide in the reaction process is remarkably reduced, the prepared lithium-sulfur battery anode material has excellent electrochemical performance, the first charge-discharge capacity can reach 1400mAh/g, the lithium-sulfur battery anode material can still keep about 1000mAh/g after being circulated for 100 times, and the lithium-sulfur battery anode material has good electrochemical performance.
(3) The cathode material for the lithium-sulfur battery provided by the invention has the advantages of low raw material price, no pollution, simple preparation method, high production efficiency and suitability for large-scale production.
Drawings
FIG. 1 is an XRD pattern of a nano-ceria/graphene/sulfur composite prepared in example 1;
FIG. 2 is a thermogravimetric plot of the nano-ceria/graphene/sulfur composite prepared in example 1;
fig. 3 is a graph of electrochemical performance of the nano-ceria/graphene/sulfur composite material prepared in example 1.
Detailed Description
Example 1
(1) Preparing graphene oxide by using a Hummers method: firstly, 1g of graphite (325 meshes) and 0.5g of NaNO are mixed3And 23mL of concentrated sulfuric acid were poured into a 250mL beaker, and 3g of KMnO4 was added to the beaker under ice-bath conditions, followed by stirring for 30min, followed by addition of 30mL of deionized water under stirring, and stirring was continued for 15 min. Then 50mL of deionized water was added again, and finally 30mL of H was added to the mixed solution2O2Obtaining graphite oxide solution (containing a large amount of H)+). Adding deionized water into the prepared graphite oxide solution, centrifuging at 6000 rpm in a centrifuge tube, removing supernatant, adding deionized water again, and separatingAnd (4) centrifuging (rotating at 6000 rpm), and repeating the operation until the pH value of the solution is 7 to finally obtain the neutral graphite oxide solution. And ultrasonically dispersing the prepared graphite oxide solution for 2 hours at normal temperature by using an ultrasonic disperser at 50kHz to obtain a graphene oxide solution, and then drying the graphene oxide solution for 24 hours in a drying oven at 60 ℃ to obtain graphene oxide powder. (ii) a
(2) A certain amount of Ce (N0) was weighed3)3·6H2O is prepared into a 0.4mol/L solution, and ammonia water is dripped until the pH value is 10. Continuously stirring for 2h, standing for 4h, filtering, washing with distilled water, and drying in an oven at 90 deg.C for 12 h;
(3) slightly grinding the dried precipitate, or directly placing into a mortar, placing into a muffle furnace, and roasting at 400 deg.C for 4h to obtain nano-cerium dioxide (particle size range of 9-32 nm);
(4) weighing a certain mass of nano sulfur powder (with the purity of 99.99 percent) and dissolving the nano sulfur powder in carbon disulfide (with the purity of 99.5 percent) to prepare a solution of 20 mg/mL;
(5) weighing the graphene oxide and the nano cerium dioxide prepared in the first step according to the mass ratio of 1:9, adding the mixture (namely the nano cerium dioxide and the graphene oxide) into deionized water according to the mass ratio of 0.01:1, and ultrasonically dispersing the mixture at 50kHz for 1h by using an ultrasonic disperser at normal temperature to obtain a graphene oxide/nano cerium dioxide uniform mixed suspension;
(6) adding the prepared carbon disulfide/sulfur solution into the graphene oxide/nano cerium dioxide uniform mixed suspension (wherein the mass ratio of graphene oxide to sulfur is 1:1), stirring for 1h at normal temperature to obtain a graphene oxide/nano cerium dioxide/sulfur mixed solution, and putting the mixed solution into a stainless steel reaction kettle to perform hydrothermal reaction for 10h at 180 ℃;
(7) and repeatedly washing the hydrogel obtained by the reaction for 3 times at 90 ℃, and carrying out vacuum freeze drying on the obtained product for 12 hours at the temperature of minus 45 ℃ and the vacuum degree of 20Pa to obtain the nano cerium dioxide/graphene/sulfur composite material.
Fig. 1 is an X-ray diffraction diagram of the nano-ceria/graphene/sulfur composite material prepared in this example. The X-ray diffraction patterns of the nano cerium dioxide and the nano cerium dioxide/graphene/sulfur composite material are respectively shown. As can be seen from the figure, the diffraction patterns are consistent without the appearance of a hetero peak, and the nano cerium dioxide sample prepared only contains fluorite-structured face-centered cubic crystals.
Fig. 2 is a thermogravimetric plot of the nano-ceria/graphene/sulfur composite material prepared in this example. As can be seen from the figure, the mass percentage of sulfur in the nano cerium dioxide/graphene/sulfur composite material is about 65%, which shows that the composite material has an excellent three-dimensional structure, has a large specific surface area and is beneficial to the storage of sulfur.
The nano cerium dioxide/graphene/sulfur composite material prepared by the method of the embodiment 1 is applied to a positive electrode material of a lithium-sulfur battery. Mixing the nano cerium dioxide/graphene/sulfur composite material obtained in example 1, a conductive agent Super P and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 8: 1:1 fully grinding and mixing to prepare slurry, uniformly coating the slurry on an aluminum foil current collector, wherein the thickness of the coating is 0.3mm, and drying the coating for 12 hours at the temperature of 60 ℃. And cutting the dried positive plate into a circular plate with the diameter of 1.5cm, and assembling the positive plate and the lithium negative plate to obtain the button type rechargeable lithium ion battery. The prepared samples were subjected to electrochemical performance analysis (BTS-5V5mA, Newway).
Fig. 3 is a graph of electrochemical performance of the nano-ceria/graphene/sulfur composite material prepared in this embodiment. As can be seen from the figure, under the 0.1C multiplying power, the first discharge capacity of the material is as high as 1400mAh/g, and the electrochemical performance of the battery is good.
Example 2
(1) Graphene oxide (same as example 1) was prepared by Hummers method;
(2) weighing a certain amount of Ce (N03)3·6H2O is prepared into a 1mol/L solution, and ammonia water is dripped until the pH value is 10. Continuously stirring for 3h, standing for 6h, filtering, washing with distilled water, and drying in an oven at 100 deg.C for 12 h;
(3) slightly grinding the dried precipitate, or directly putting the precipitate into a mortar, putting the mortar into a muffle furnace, and roasting for 6h at 300 ℃ to obtain nano cerium dioxide;
(4) weighing a certain mass of nano sulfur powder (with the purity of 99.99 percent) and dissolving the nano sulfur powder in carbon disulfide (with the purity of 99.5 percent) to prepare a solution of 20 mg/mL;
(5) weighing the graphene oxide and the nano cerium dioxide prepared in the first step according to the mass ratio of 1:15, adding the mixture into deionized water according to the mass ratio of 0.01:1, and ultrasonically dispersing the mixture at 50kHz for 2 hours by using an ultrasonic disperser at normal temperature to obtain a graphene oxide/nano cerium dioxide uniformly-mixed suspension;
(6) adding the prepared carbon disulfide/sulfur solution (wherein the mass ratio of graphene oxide to sulfur is 1:1) into the graphene oxide/nano cerium dioxide uniform mixed suspension, stirring for 1h at normal temperature to obtain a graphene oxide/nano cerium dioxide/sulfur mixed solution, and putting the mixed solution into a stainless steel reaction kettle to carry out hydrothermal reaction for 12h at 180 ℃;
(7) and repeatedly washing the hydrogel obtained by the reaction for 3 times at 90 ℃, and carrying out vacuum freeze drying on the obtained product for 12 hours at the temperature of minus 45 ℃ and the vacuum degree of 20Pa to obtain the nano cerium dioxide/graphene/sulfur composite material.
Example 3
(1) Graphene oxide (same as example 1) was prepared by Hummers method;
(2) weighing a certain amount of Ce (N03)3·6H2O is prepared into a solution of 2mol/L, and ammonia water is dripped until the pH value is 10. Continuously stirring for 5h, standing for 8h, filtering, washing with distilled water, and drying in an oven at 110 deg.C for 12 h;
(3) slightly grinding the dried precipitate, or directly putting the precipitate into a mortar, putting the mortar into a muffle furnace, and roasting at 450 ℃ for 8h to obtain nano cerium dioxide;
(4) weighing a certain mass of nano sulfur powder (with the purity of 99.99 percent) and dissolving the nano sulfur powder in carbon disulfide (with the purity of 99.5 percent) to prepare a solution of 20 mg/mL;
(5) weighing the graphene oxide and the nano cerium dioxide prepared in the first step according to the mass ratio of 1:9, adding the mixture into deionized water according to the mass ratio of 0.01:1 of the mixture to the deionized water, and ultrasonically dispersing the mixture at 50kHz for 1h by using an ultrasonic disperser at normal temperature to obtain a graphene oxide/nano cerium dioxide uniformly-mixed suspension;
(6) adding the prepared carbon disulfide/sulfur solution (wherein the mass ratio of graphene oxide to sulfur is 1:2) into the graphene oxide/nano cerium dioxide uniform mixed suspension, stirring for 1h at normal temperature to obtain a graphene oxide/nano cerium dioxide/sulfur mixed solution, and putting the mixed solution into a stainless steel reaction kettle to carry out hydrothermal reaction for 24h at 150 ℃;
(7) and repeatedly washing the hydrogel obtained by the reaction for 3 times at 90 ℃, and carrying out vacuum freeze drying on the obtained product for 12 hours at the temperature of minus 45 ℃ and the vacuum degree of 20Pa to obtain the nano cerium dioxide/graphene/sulfur composite material.
The invention is not the best known technology.
Claims (3)
1. A preparation method of a nano cerium dioxide/graphene/sulfur composite material is characterized by comprising the following steps:
the first step is as follows: dissolving nano sulfur powder in carbon disulfide to prepare 2-30mg/mL carbon disulfide/sulfur solution;
the second step is that: respectively adding graphene oxide and nano cerium dioxide into deionized water, and ultrasonically dispersing the solution for 1-3 hours at normal temperature by using an ultrasonic dispersion instrument to obtain a graphene oxide/nano cerium dioxide mixed suspension;
wherein, the mass ratio of graphene oxide: nano ceria =1:1-20, sum of the mass of graphene oxide and nano ceria: deionized water mass =0.001-0.03: 1;
the third step: adding the prepared carbon disulfide/sulfur solution into the graphene oxide/nano cerium dioxide mixed suspension, stirring for 1-3h at normal temperature to obtain a graphene oxide/nano cerium dioxide/sulfur mixed solution, putting the mixed solution into a stainless steel reaction kettle, and carrying out hydrothermal reaction for 5-24h at the temperature of 100 ℃ and 200 ℃; then washing the hydrogel obtained by the reaction for 2-6 times at 60-110 ℃ by using deionized water, and carrying out vacuum freeze drying on the obtained product for 5-12h at-45 ℃ to obtain the nano cerium dioxide/graphene/sulfur composite material;
wherein, the mass ratio of graphene oxide: sulfur =1: 1-5.
2. The method for preparing nano ceria/graphene/sulfur composite according to claim 1, wherein the power of the ultrasonic disperser in the second step is 35-60 kHz.
3. The method for preparing nano-ceria/graphene/sulfur composite according to claim 1, wherein the vacuum degree of vacuum drying in the third step is 20 Pa.
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| CN108807947B (en) * | 2018-08-07 | 2021-07-27 | 河源广工大协同创新研究院 | Preparation method of lithium-sulfur battery positive electrode material |
| CN109599539B (en) * | 2018-11-01 | 2021-10-22 | 宁波中科孚奇能源科技有限公司 | Carbon-sulfur composite positive electrode and preparation method and application thereof |
| CN110723727B (en) * | 2019-09-12 | 2021-05-11 | 齐鲁工业大学 | Pine-branch-shaped samarium oxide graphene sulfur gel structural material, and preparation method and application thereof |
| CN111092206B (en) * | 2019-12-19 | 2022-08-16 | 佛山科学技术学院 | CeO (CeO) 2 Preparation method of lithium-sulfur battery made of TpBD/S material |
| CN111740114B (en) * | 2020-07-02 | 2021-07-02 | 四川大学 | Lithium-sulfur battery composite positive electrode material and preparation method thereof |
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Application publication date: 20180223 Assignee: Heyuan Qiangxin Energy Technology Co.,Ltd. Assignor: SYNERGY INNOVATION INSTITUTE OF GDUT, HEYUAN Contract record no.: X2023980036111 Denomination of invention: A preparation method of nano Cerium(IV) oxide/Graphene/sulfur composite Granted publication date: 20201103 License type: Common License Record date: 20230531 |