Zeolite-based positive pole material for lithium-sulfur battery and preparation and application methods thereof

A lithium-sulfur battery and positive electrode material technology, which is applied in the direction of battery electrodes, lithium batteries, non-aqueous electrolyte battery electrodes, etc., can solve problems such as capacity fading, battery negative electrode corrosion, battery internal resistance, sulfur electrode microcracks, etc.

Inactive Publication Date: 2014-04-09
XIANGTAN UNIV
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  • Claims
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Problems solved by technology

[0003] Nevertheless, lithium-sulfur batteries still have the following three problems: (1) Lithium polysulfide produced during charging and discharging of lithium-sulfur batteries is easily soluble in organic electrolyte, which gradually reduces the active material of the electrode, and due to the shuttle principle, the dissolved Lithium polysulfide will pass through the separator and reach the lithium sheet of the negative electrode of the battery. The resulting lithium sulfide and other products have poor conductivity and are insoluble, which will cause corrosion of the negative electrode of the battery and increase the internal resistance of the battery, resulting in poor cycle performance of the battery and gradual increase in capacity. attenuation
(2) The conductivity of sulfur is poor, which is not conducive to the high rate performance of the battery. It is impossible to charge and discharge the Li / S battery with 100% sulfur as the positive electrode at room temperature. This is because the ionic conductivity and electronic conductivity of sulfur are very low. It leads to poor electrochemical performance and low utilization rate of sulfur in the electrode. Generally, compounding sulfur with carbon or other conductive materials can solve the problem of poor conductivity.
(3) During the charging and discharging process of sulfur, the expansion and shrinkage of the volume is very large, which may cause battery damage, because during the cycle, the volume deformation of the sulfur electrode in the lithium-sulfur battery is as high as 22%, which may cause microcracks inside the sulfur electrode
The existence of such microcracks and the formation of the insulating phase Li2S in the cracks destroy the integrity of the electrode, which eventually aggravates the capacity fading of lithium-sulfur batteries.

Method used

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  • Zeolite-based positive pole material for lithium-sulfur battery and preparation and application methods thereof
  • Zeolite-based positive pole material for lithium-sulfur battery and preparation and application methods thereof
  • Zeolite-based positive pole material for lithium-sulfur battery and preparation and application methods thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0037] Pretreatment of zeolite powder: select zeolite powder with a particle size of less than 5 μm, wash it with deionized water, then ultrasonically vibrate the cleaned zeolite powder for 1 hour, and then dry it in an oven at 85° C. for 24 hours. Add the zeolite powder to 10mol / L HCl solution for pickling treatment for 2 hours, and then perform preactivation, keep the zeolite powder at 200°C for 2 hours under vacuum condition, and cool it to room temperature under vacuum condition to obtain the purified zeolite powder material.

[0038] Mix the zeolite powder material and elemental sulfur 1:1 evenly after the above pretreatment, place in a quartz boat, heat to 100°C at 2°C / min under a vacuum of 100Pa, keep the temperature for 2h, and then continue to mix the sample Heating to 120°C at a heating rate of 2°C / min, keeping the temperature at a constant temperature for 0.5h, maintaining the vacuum condition and then cooling down to room temperature at a cooling rate of 2°C / min. The...

Embodiment 2

[0040] Select the zeolite sulfur-carrying material obtained in Example 1 to prepare the nickel-coated zeolite sulfur-carrying material:

[0041] Pretreatment is carried out on the zeolite sulfur-loaded material to ensure that the coated metal is coated evenly and has good adhesion.

[0042] 1. Degreasing: Take 5g of zeolite sulfur-loaded material in 200ml of ethanol solution, add 100ml of 37% HCl, ultrasonically oscillate for 20min at a temperature of 30°C, wash with deionized water until the pH is neutral, and filter to dry.

[0043] 2. Sensitization: the above-mentioned zeolite sulfur-loaded material was mixed with 10g / L SnCl 2 2H 2 Carry out sensitization treatment in O+40g / L HCL solution for 30min, wash with deionized water, and filter dry.

[0044] 3. Activation: Put the sensitized zeolite sulfur-loaded material in 0.5g / L PdCl 2 +0.25mL HCl solution for activation treatment for 30min, washed with deionized water, and filtered dry.

[0045] 4. Reduction: soak the activ...

Embodiment 3

[0055] The process of pretreating the zeolite powder is the same as in Example 1.

[0056] Mix the pretreated zeolite material with elemental sulfur 1:1 evenly, place it in a quartz boat, heat it to 155°C in a tube furnace fed with Ar gas, keep the temperature constant for 12 hours, continue to heat the mixed sample to 320°C, and keep the temperature constant for 6 hours , maintain the protective atmosphere conditions and cool to room temperature. The samples were further ground and dried to prepare zeolite sulfur-loaded materials.

[0057] Preparation of copper-coated zeolite sulfur-carrying material: preparation was carried out by the same steps as in Example 2, except that the following solution composition and process were used for reduction and electroless plating.

[0058] Reduction: soak the activated zeolite sulfur-loaded material in 10% formaldehyde solution for 0.5-2min, wash with deionized water, and filter to dry.

[0059] Electroless copper cladding:

[0060] T...

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Abstract

The invention discloses a zeolite-based positive pole material for a lithium-sulfur battery and preparation and application methods thereof. According to the positive pole material, zeolite is used as a skeleton, and a sulfur-loaded composite material is obtained through infusing elemental sulfur to zeolite and then is wrapped with a conductive substance. According to the zeolite-based positive pole material for the lithium-sulfur battery and the preparation and application methods thereof, through compounding zeolite and sulfur, the dissolution of polysulfide can be effectively reduced, and the volume expansion of sulfur during charging/discharging can be effectively inhibited, so that the cycling performance of the lithium-sulfur battery is improved; due to the wrapping of the conductive substance, the conductivity of the material is enhanced, and the capacity of the lithium-sulfur battery is increased. The preparation process of the positive pole material is simple, and zeolite belongs to a natural environment-friendly material and is low in cost, so that the industrialization of the lithium-sulfur battery is facilitated; meanwhile, due to the introduction of zeolite, the industrial transformation and upgrading of nonmetallic minerals are promoted.

Description

technical field [0001] The invention belongs to the field of new energy materials, and in particular relates to a zeolite-based lithium-sulfur battery cathode material and a preparation and application method thereof. Background technique [0002] With the increasingly serious environmental pollution and the continuous aggravation of the energy crisis, the development of high energy density, low-cost renewable energy systems has gradually become the focus of people's research. Elemental sulfur is considered to be an excellent cathode material for lithium batteries due to its high specific capacity, low price, environmental friendliness, and light density. Lithium-sulfur batteries use elemental sulfur as the positive electrode reaction material and metal lithium as the negative electrode, and the theoretical energy density can reach 2600Wh / kg. Compared with conventional lithium-ion batteries, lithium-sulfur batteries are able to achieve 3 to 5 times their energy density, and...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): H01M4/13H01M4/36H01M4/62H01M4/139
CPCY02E60/122H01M4/13H01M4/139H01M4/362H01M4/62H01M4/624H01M10/052Y02E60/10
Inventor 谢淑红潘俊安潘勇朱岭欧云徐海平刘丽媚伍成
Owner XIANGTAN UNIV
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