CN109994721B - S-Ni-O-C bonding enhancement-based lithium-sulfur battery composite positive electrode material and preparation method thereof - Google Patents

S-Ni-O-C bonding enhancement-based lithium-sulfur battery composite positive electrode material and preparation method thereof Download PDF

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CN109994721B
CN109994721B CN201910231906.7A CN201910231906A CN109994721B CN 109994721 B CN109994721 B CN 109994721B CN 201910231906 A CN201910231906 A CN 201910231906A CN 109994721 B CN109994721 B CN 109994721B
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biochar
positive electrode
electrode material
composite positive
sulfur
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CN109994721A (en
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雷维新
夏鹏涛
张琪悦
王旭日
夏爽
马颖妍
潘勇
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Xiangtan University
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    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
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    • 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
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Abstract

The invention provides an S-Ni-O-C bonding enhanced lithium-sulfur battery composite positive electrode material and a preparation method thereof. The composite cathode material provided by the invention can retain the high specific surface area of a biochar framework, can provide polar adsorption sites of transition metal elements on the biochar surface, and can establish chemical bond connection between a sulfur cathode and biochar, so that the stability of an active material is effectively improved, and the electrochemical performance of the electrode material is finally improved.

Description

S-Ni-O-C bonding enhancement-based lithium-sulfur battery composite positive electrode material and preparation method thereof
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a lithium-sulfur battery composite positive electrode material based on S-Ni-O-C bonding reinforcement and a preparation method thereof.
Background
The growing demand of the current society for high energy consumption applications such as low energy consumption electric vehicles and smart grid storage systems has led to the continuous search of the scientific community for novel battery systems beyond the traditional lithium ion batteries, therefore, lithium-sulfur (L i-S) batteries based on the oxidation-reduction reaction between elemental sulfur and lithium metal are of great interest due to their inherent high theoretical energy density (2600 Wh/Kg).
Although lithium-sulfur batteries have many advantages such as large capacity, easy processing, and low cost, the new battery system has not been commercialized to date. The insulation of sulfur, the volume expansion effect existing during the charge-discharge cycle of the electrode material, and the shuttle effect caused by the dissolution of polysulfide in the electrolyte, seriously hinder the full application of high-capacity sulfur cathode materials. An effective solution to the above problems is to design an ideal sulfur positive electrode framework material, to improve the conductivity of the positive electrode material, and to alleviate the volume expansion problem during the reaction process. The porous biomass charcoal material becomes the most interesting sulfur positive electrode framework material due to high conductivity, high specific surface area and rich pore structure. However, the porous biomass charcoal is a non-polar material, and therefore cannot effectively adsorb polysulfide, which causes that polysulfide is easily dissolved in electrolyte in the charging and discharging processes of the lithium-sulfur battery, and reduces the cycle performance of the battery. Therefore, polar modification is needed to the nonpolar porous biomass charcoal skeleton to enhance the adsorption of the material to polysulfide.
Recently, Chen et al (Chen et al, Nano letters,2016,17(1):437-444.) and L iu et al (L iuet al, Advanced Materials,2018,30(12):1706895.) successively reported a Co-doped lithium-sulfur battery positive electrode material using a zinc/cobalt bimetallic zeolite imidazole framework material (ZIF-67) as a raw material, which confirmed that a transition metal element has a strong affinity with sulfur/polysulfide and is easy to generate a chemical combination reaction.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a lithium-sulfur battery composite positive electrode material enhanced based on S-Ni-O-C bonding, which not only can keep the high specific surface area of a biochar framework, but also can provide polar adsorption sites of transition metal elements on the biochar surface, and simultaneously can establish chemical bond connection between a sulfur positive electrode and biochar, thereby effectively improving the stability of an active material and finally improving the electrochemical performance of the electrode material.
The invention also aims to provide a preparation method of the lithium-sulfur battery composite positive electrode material, which has the advantages of wide material source, low cost, simple process and good repeatability.
In order to achieve the purpose, the invention provides a lithium-sulfur battery composite positive electrode material based on S-Ni-O-C bonding reinforcement, biochar is used as a carrier, polar oxygen-containing functional groups are grafted on the surface of the biochar, nano nickel particles are loaded on the surface of the biochar to form a Ni-O-C structure, and then sulfur fixation is carried out to obtain the S-Ni-O-C bonding reinforcement lithium-sulfur battery composite positive electrode material.
Preferably, the Ni-O-C content in the cathode material is 20-30 wt%.
Preferably, the particle size of the nano nickel particles is 5-20 nm, and the mass content of the nano nickel particles accounts for 5-10 wt% of the adopted biochar.
Preferably, the sulfur content in the cathode material is 70-80 wt%.
The invention also provides a preparation method of the lithium-sulfur battery composite positive electrode material, which specifically comprises the following steps:
(1) the specific surface area is 2000-4000 m2Mixing and stirring the biochar per gram and the Triton X-100 solution, and filtering to obtain biochar with the surface enriched with polar oxygen-containing functional groups;
(2) loading the nano nickel particles on the biochar with the surface enriched with polar oxygen-containing functional groups in the step (1) to obtain a biochar material C-O-Ni with the surface uniformly dispersed with the nano nickel particles;
(3) and (3) mixing and grinding the biochar material C-O-Ni and the sublimed sulfur in the step (2), and drying in vacuum at 150-165 ℃ to obtain the S-Ni-O-C bonding enhanced lithium-sulfur battery composite positive electrode material.
Preferably, the method comprises the steps of taking a leaf material of a Chinese irontree as a raw material, performing primary carbonization on the raw material at 300-450 ℃ by adopting a two-step carbonization method, uniformly mixing the raw material subjected to primary carbonization and potassium hydroxide according to the mass ratio of 1: 2-1: 4, activating at the temperature of 750-800 ℃ for 0.5-1.5 h, washing with acid and deionized water, and filtering to obtain the product with the specific surface area of 2000-4000 m2High specific surface area biochar per gram.
A high specific surface area means that the material possesses a larger pore volume that will hold more sulfur/polysulfide, making the biomass carbon matrix material an active sulfur reservoir and reactor for physical and chemical adsorption of polysulfides.
Preferably, the solid-liquid ratio of the biochar to the triton X-100 solution is 1: 200-400, and the mass fraction of the triton X-100 solution is 1-5 wt%. The invention mixes and stirs the nonpolar material high specific surface area biochar and the triton X-100 solution to obtain the high specific surface area biochar with the triton X-100 adhered on the surface, and simultaneously means that the surface of the high specific surface area biochar substrate is enriched with oxygen-containing functional groups.
Preferably, the nano nickel particle load is subjected to chemical nickel plating on the surface of the biochar by adopting a chemical nickel plating technology, so that the biochar material C-O-Ni with the nano nickel particles uniformly dispersed on the surface is obtained. After the surface of the biochar substrate is grafted with the oxygen-containing functional group, the surface chemical nickel plating of the biochar substrate can be carried out by utilizing a surface chemical nickel plating technology, and NiSO4、Na3C6H5O7、(NH4)2SO4、NaH2PO2And mixing the NaOH mixed solution with the biochar enriched with oxygen-containing functional groups, then condensing and refluxing, plating for 5-15 min, and after plating is finished, obtaining the biochar material C-O-Ni with the surface uniformly dispersed with the nano nickel particles and the high specific surface area.
Preferably, the mass ratio of the charcoal material C-O-Ni to the sublimed sulfur is 1: 4-3: 7.
The invention also provides a lithium-sulfur battery, which is prepared by mixing the positive electrode material S-Ni-O-C, acetylene black and PVDF to prepare slurry, coating the slurry on an aluminum foil, pressing the slurry into a battery positive electrode piece after vacuum drying, and assembling the battery.
According to the invention, biomass carbon with high specific surface area is used as a carrier, a nonionic surfactant Triton X-100 is added to graft polar oxygen-containing functional groups on the surface of the biomass carbon, nickel elements are uniformly dispersed on the surface of the biomass carbon by using a chemical bond bonding mode and a surface chemical plating technology to form a Ni-O-C structure, and meanwhile, an S-Ni-O-C anode material is further generated by using the affinity of transition metal nickel elements to sulfur. The positive electrode material takes biomass carbon with high specific surface area as a matrix, combines Ni-O polar groups, can adsorb polar polysulfide from two aspects of physical and chemical adsorption, effectively inhibits the dissolution of polysulfide, and greatly improves the cycling stability of the lithium-sulfur battery.
Drawings
FIG. 1 is a pore size distribution diagram of the high specific surface area biochar prepared in example 1;
as can be seen from FIG. 1, the biochar substrate used in the invention has a small overall pore size, the pore size distribution is 1-5nm, and the pore size distribution is 1.43cm3The ultra-large pore volume per gram can contain more sulfur element;
FIG. 2 is an X-ray diffraction (XRD) pattern of biochar, C-O-Ni, S-Ni-O-C in example 1, in which the abscissa is the scanning range (2-Theta) and the ordinate is the diffraction intensity (intsitya. u.);
FIG. 2 shows the diffraction pattern and S of the biochar substrate8As can be seen by the comparison of the standard spectrogram, the S-Ni-O-C composite material is prepared by the method;
FIG. 3 is a scanned graph of C-O-Ni material prepared in example 1;
as can be seen from fig. 3, the fine nanoparticles in the square frame are nickel elements uniformly distributed, and the multi-point scanning result shows that the nickel nanoparticles are uniformly distributed on the entire surface of the biochar substrate;
FIG. 4 is a scanned image of the S-Ni-O-C composite based on bonding enhancement made in example 1;
as can be seen from fig. 4, compared with the scanned graph of fig. 3, the surface of the composite material is smoother, which is confirmed to be a sulfur-coated state, and a biochar substrate and sulfur element are formed to be mutually infiltrated and blended (a part of sulfur element is infiltrated into the porous carbon material), and numerous nickel nanoparticles are uniformly dispersed between the biochar substrate and the sulfur element;
FIG. 5 is a cycle test chart of the S-Ni-O-C cathode material prepared in example 1.
Detailed Description
The invention is further illustrated by the following figures and examples. The following examples are intended to further illustrate the invention, but not to limit it.
Example 1
(1) Selecting a leaf material of a Chinese irontree, carrying out primary carbonization at 400 ℃, and then mixing the carbonized leaf material with KOH according to the mass ratio of 1:3Activating the mixture for 1 hour at 800 ℃ in a tubular furnace in proportion, and then obtaining the product with the specific surface area of 2700m after acid washing and deionized water repeated suction filtration2High specific surface area biochar per gram.
(2) Selecting the material with the specific surface area of 2700m2Putting the biochar with high specific surface area per gram and triton X-100 diluted to 5 per thousand in 500ml of solution, carrying out ultrasonic oscillation and stirring for 1h, and then carrying out suction filtration to obtain the biochar with high specific surface area and enriched with oxygen-containing functional groups on the surface.
(3) The components of the plating solution are 0.02 mol/L NiSO40.03 mol/L of Na3C6H5O70.035 mol/L of (NH)4)2SO40.08 mol/L of NaH2PO20.05 mol/L NaOH, 2 g/L high specific surface biochar with oxygen-containing functional groups enriched on the surface, putting the biochar into a three-neck flask together, heating in water bath at 60 ℃, refluxing by a condenser pipe, magnetically stirring, plating for 20min, washing with water and drying to obtain the C-O-Ni material, as shown in figure 3.
(4) Mixing and grinding the C-O-Ni and the sublimed sulfur according to the mass ratio of 1:4, then placing the mixture into a small reaction kettle isolated from oxygen, placing the reaction kettle into a vacuum drying box, and drying the mixture at the constant temperature of 155 ℃ for 20 hours to obtain the S-Ni-O-C composite cathode material based on bonding reinforcement, wherein the S-Ni-O-C composite cathode material is shown in figure 4.
The assembled battery is subjected to a cyclic charge-discharge test at a current density of 0.5C, and the voltage range is 1.5-3.0V. The cycle chart is shown in fig. 5: the first discharge capacity is 1329mAh/g, after 100 times of circulation, the discharge capacity is 1110mAh/g, and after the initial 3 times of circulation stabilization, the single-turn capacity attenuation rate is only 0.018%; after 300 cycles, the discharge capacity is 923mAh/g, and the stable one-turn capacity fading rate is 0.062%.
Comparative example 1
(1) Selecting a leaf material of a Chinese irontree, carrying out primary carbonization at 400 ℃, then activating the leaf material and KOH for 1h at the temperature of 800 ℃ in a tubular furnace according to the mass ratio of 1:3, and then carrying out acid pickling and repeated suction filtration of deionized water to obtain the product with the specific surface area of 2700m2High specific surface area biochar per gram.
(2) The specific surface area is 2700m2High in/gDirectly mixing and grinding the biochar with the sublimed sulfur according to the mass ratio of 1:4, then placing the mixture in a small reaction kettle isolated from oxygen in a vacuum drying box, and drying at the constant temperature of 155 ℃ for 20 hours to obtain the S/C composite cathode material based on the biochar with the high specific surface area.
The assembled battery is subjected to a cyclic charge-discharge test at a current density of 0.5C, and the voltage range is 1.5-3.0V. The first discharge capacity is 1279mAh/g, after 100 cycles, the discharge capacity is 515mAh/g, and after the initial 3 cycles are stable, the single-circle capacity decay rate is 0.454 percent.
Comparative example 2
(1) Selecting a leaf material of a Chinese irontree, carrying out primary carbonization at 400 ℃, then activating the leaf material and KOH in a tubular furnace at the temperature of 800 ℃ for 1h according to the mass ratio of 1:1, and then carrying out acid pickling and repeated suction filtration of deionized water to obtain the product with the specific surface area of 1800m2Biochar per gram.
(2) The specific surface area is 1800m2Putting the biochar per gram and triton X-100 diluted to 5 per thousand in 500ml of solution, carrying out ultrasonic oscillation and stirring for 1 hour, and then carrying out suction filtration to obtain the biochar with oxygen-containing functional groups enriched on the surface.
(3) The components of the plating solution are 0.02 mol/L NiSO40.03 mol/L of Na3C6H5O70.035 mol/L of (NH)4)2SO40.08 mol/L of NaH2PO20.05 mol/L of NaOH and 2 g/L of biochar with high specific surface area and rich oxygen-containing functional groups on the surface are placed in a three-neck flask together, heated in water bath at 60 ℃, refluxed by a condenser tube, magnetically stirred, plated for 20min, washed and dried to obtain the C-O-Ni material.
(4) Mixing and grinding C-O-Ni and sublimed sulfur according to the mass ratio of 1:4, then placing the mixture in a small reaction kettle isolated from oxygen in a vacuum drying box, drying the mixture for 20 hours at the constant temperature of 155 ℃, and obtaining the S-Ni-O-C composite cathode material based on bonding reinforcement
The assembled battery is subjected to a cyclic charge-discharge test at a current density of 0.5C, and the voltage range is 1.5-3.0V. The first discharge capacity is 804mAh/g, the capacity is kept to be 459mAh/g after 100 cycles, and the single-turn capacity fading rate is 0.335% after the initial 4 cycles are stable.
Comparative example 3
(1) Selecting a leaf material of a Chinese irontree, carrying out primary carbonization at 400 ℃, then activating the leaf material and KOH in a tubular furnace at the temperature of 800 ℃ for 1h according to the mass ratio of 1:1, and then carrying out acid pickling and repeated suction filtration of deionized water to obtain the product with the specific surface area of 1800m2Biochar per gram.
(2) The specific surface area is 1800m2And (2) directly mixing and grinding the biochar/g and sublimed sulfur according to the mass ratio of 1:4, then placing the mixture in a small reaction kettle isolated from oxygen, placing the reaction kettle in a vacuum drying box, and drying the mixture at the constant temperature of 155 ℃ for 20 hours to obtain the S/C composite cathode material based on the biochar.
The assembled battery is subjected to a cyclic charge-discharge test at a current density of 0.5C, and the voltage range is 1.5-3.0V. The first discharge capacity is 820mAh/g, after 100 cycles, the discharge capacity is 287mAh/g, and after the initial 4 cycles are stable, the single-circle capacity decay rate is 0.559%.
Comparative example 4
(1) Selecting a leaf material of a Chinese irontree, carrying out primary carbonization at 400 ℃, then activating the leaf material and KOH for 1h at the temperature of 800 ℃ in a tubular furnace according to the mass ratio of 1:3, and then carrying out acid pickling and repeated suction filtration of deionized water to obtain the product with the specific surface area of 2700m2High specific surface area biochar per gram.
(2) The components of the plating solution are 0.02 mol/L NiSO40.03 mol/L of Na3C6H5O70.035 mol/L of (NH)4)2SO40.08 mol/L of NaH2PO20.05 mol/L NaOH and 2 g/L high specific surface area biochar are placed in a three-neck flask together, heated in water bath at 60 ℃, refluxed by a condenser pipe, magnetically stirred, plated for 20min, washed and dried to obtain the C-Ni material.
(3) Mixing and grinding the C-Ni and the sublimed sulfur according to the mass ratio of 1:4, then placing the mixture in a small reaction kettle isolated from oxygen in a vacuum drying box, and drying the mixture at the constant temperature of 155 ℃ for 20 hours to obtain the S-Ni-C composite cathode material based on bonding reinforcement.
The assembled battery is subjected to a cyclic charge-discharge test at a current density of 0.5C, and the voltage range is 1.5-3.0V. The first discharge capacity is 1320mAh/g, after 100 cycles, the discharge capacity is 757mAh/g, after the initial 4 cycles are stable, the single-circle capacity attenuation rate is 0.268%.

Claims (10)

1. A lithium-sulfur battery composite positive electrode material based on S-Ni-O-C bonding reinforcement is characterized in that: the biochar is taken as a carrier, the surface of the biochar is grafted with polar oxygen-containing functional groups, nano nickel particles are loaded on the surface of the biochar to form a Ni-O-C structure, and sulfur fixation is carried out to obtain the S-Ni-O-C bonding enhanced lithium-sulfur battery composite positive electrode material.
2. The composite positive electrode material according to claim 1, characterized in that: the Ni-O-C content in the anode material is 20-30 wt%.
3. The composite positive electrode material according to claim 1, characterized in that: the particle size of the nano nickel particles is 5-20 nm, and the mass content of the nano nickel particles accounts for 5-10 wt% of the adopted biochar.
4. The composite positive electrode material according to claim 1, characterized in that: the sulfur content of the positive electrode material is 70-80 wt%.
5. The method for preparing a composite positive electrode material according to any one of claims 1 to 4, comprising the steps of:
(1) the specific surface area is 2000-4000 m2Mixing and stirring the biochar per gram and the Triton X-100 solution, and filtering to obtain biochar with the surface enriched with polar oxygen-containing functional groups;
(2) loading the nano nickel particles on the biochar with the surface enriched with polar oxygen-containing functional groups in the step (1) to obtain a biochar material C-O-Ni with the surface uniformly dispersed with the nano nickel particles;
(3) and (3) mixing and grinding the biochar material C-O-Ni and the sublimed sulfur in the step (2), and drying in vacuum at 150-165 ℃ to obtain the S-Ni-O-C bonding enhanced lithium-sulfur battery composite positive electrode material.
6. The method of claim 5, wherein: taking a leaf material of a Chinese irontree as a raw material, adopting a two-step carbonization method, firstly carrying out primary carbonization on the raw material at 300-450 ℃, then uniformly mixing the raw material subjected to primary carbonization and potassium hydroxide according to a mass ratio of 1: 2-1: 4, activating at the temperature of 750-800 ℃ for 0.5-1.5 h, washing with acid, washing with deionized water, and filtering to obtain the product with the specific surface area of 2000-4000 m2Biochar per gram.
7. The method of claim 5, wherein: the solid-liquid ratio of the biochar to the triton X-100 solution is 1: 200-400, and the mass fraction of the triton X-100 solution is 1-5 wt%.
8. The method of claim 5, wherein: the nano nickel particle load adopts a surface chemical nickel plating technology to carry out surface chemical nickel plating on the biochar, so as to obtain the biochar material C-O-Ni with the nano nickel particles uniformly dispersed on the surface.
9. The method of claim 5, wherein: the mass ratio of the charcoal material C-O-Ni to the sublimed sulfur is 1: 4-3: 7.
10. A lithium sulfur battery produced using the composite positive electrode material according to any one of claims 1 to 4 or the composite positive electrode material produced by the production method according to any one of claims 5 to 9.
CN201910231906.7A 2019-03-26 2019-03-26 S-Ni-O-C bonding enhancement-based lithium-sulfur battery composite positive electrode material and preparation method thereof Expired - Fee Related CN109994721B (en)

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