CN102185158A - Lithium sulfur battery provided with adsorption layer - Google Patents
Lithium sulfur battery provided with adsorption layer Download PDFInfo
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- CN102185158A CN102185158A CN2011100928172A CN201110092817A CN102185158A CN 102185158 A CN102185158 A CN 102185158A CN 2011100928172 A CN2011100928172 A CN 2011100928172A CN 201110092817 A CN201110092817 A CN 201110092817A CN 102185158 A CN102185158 A CN 102185158A
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Abstract
The invention relates to a lithium sulfur battery provided with an adsorption layer. The adsorption layer is added in the lithium sulfur battery, is made of a strong-adsorption material with a high specific surface area and a porous structure, and is positioned between an anode pole piece and a porous diaphragm. The adsorption layer can adsorb polysulfide formed in charging and discharging processes of the lithium sulfur battery and prevent the polysulfide dissolved in electrolytic solution from scattering to the surface of a cathode to generate corrosion reaction with lithium and cause irreversible capacity losses of the battery. Therefore, the adsorption layer can improve the performance of the lithium sulfur battery.
Description
Technical field
The present invention relates to the lithium-sulfur cell technical field, particularly a kind of have an adsorption layer
Technical background
Positive electrode is the bottleneck of restriction lithium battery development always, and present business-like lithium battery active material mainly is LiCoO
2, LiMnO
4Deng.The phase anticathode, business-like positive electrode specific energy is too low, LiCoO
2Specific capacity be 130～140mAh/g, LiMnO
4Specific capacity be 110～130mAh/g, and they cost an arm and a leg.Therefore develop novel green energy storage positive electrode and just seem particularly crucial and urgent with high-energy-density, low cost and long circulation life.
Elemental sulfur has advantages such as height ratio capacity, cheap, hypotoxicity as positive electrode.The theoretical specific capacity of elemental sulfur is 1675mAh/g, and theoretical specific energy is 2600Wh/Kg, is that specific capacity is the highest in the positive electrode of being understood at present, is far longer than business-like secondary cell of present stage.Moreover, the operating voltage of lithium-sulfur cell can satisfy the application demand of present multiple occasion about 2.1V, and the low price of elemental sulfur, source are abundant, and therefore the research and development around lithium-sulfur cell and critical material thereof receive much concern.Though lithium-sulfur cell uses elemental sulfur to have lot of advantages such as specific capacity height, cost are low as positive electrode, but problem such as exist poor electric conductivity, capacity attenuation is fast and cycle life is short, and exist because of many lithium sulfides and in electrolyte, dissolve " the flying the shuttle phenomenon " that causes.
Studies show that the main cause of lithium-sulfur cell capacity attenuation is the destruction of electrode structure pattern.In the process of discharge, elemental sulfur at first is reduced and generates the solubility polysulfide, the intermediate product polysulfide of discharge process dissolves in electrolyte easily, cause the enclosed pasture efficient of battery charging and discharging to reduce, and its can along with electrolyte be diffused into negative terminal surface and with lithium generation corrosion reaction, cause irreversible capacitance loss.And along with the carrying out of discharge process, the solubility polysulfide can finally be reduced into Li
2S and Li
2S
2Li
2S and Li
2S
2The conductivity extreme difference, its can cover the surface of positive electrode active materials with the form of solid film, hinders the electrochemical reaction between electrolyte and electrode active material.
In order to improve the cycle performance of lithium-sulfur cell, the present invention adds an adsorption layer in existing battery structure, in order to adsorb the polysulfide that lithium-sulfur cell produces in charge and discharge process, stop polysulfide to move to negative pole with electrolyte, suppress the generation of " flying the shuttle phenomenon ", thereby improve the performance and the useful life of lithium-sulfur cell.
Summary of the invention
The purpose of this invention is to provide a kind of preparation of the positive pole plate of lithium-sulfur cell that adds adsorption layer and contain the lithium-sulfur cell of anode pole piece of the present invention.
Traditional lithium-sulfur cell structure mainly comprises positive pole, negative pole and porous septum.In order to improve the easily dissolving and be diffused into negative pole with electrolyte and cause problems such as battery capacity decay, cycle performance reduction in electrolyte of lithium-sulfur cell intermediate product polysulfide, the present invention has added adsorption layer in the lithium-sulfur cell structure.
Adsorption layer of the present invention is between anode pole piece and porous septum, the adsorption layer material selection has high-specific surface area, the porous material of good adsorption properties, as active carbon, carbosphere, mesoporous carbon, carbide derived carbon (pore-size distribution 0.5～5nm), carbon molecular sieve, palygorskite-sepiolite group mineral fibres, diatomite or and polymeric adsorbent etc.Wherein, palygorskite-sepiolite group mineral fibres is mainly palygorskite and sepiolite.Sorbing material depends primarily on Surface Physical and chemical constitution to the absorption of adsorption molecule.Sorbing material also is divided into two kinds of physical absorption and chemisorbed to the absorption of adsorbate.Physical absorption is owing to Van der Waals force causes, chemisorbed then is that the chemical bond power effect between adsorbent surface and the adsorbate causes that most of adsorption processes are physical absorption.
Van der Waals force has the sorbing material of loose structure and high surface owing to can form powerful absorption field at material surface, after adsorbate is adsorbed in the aperture structure of sorbing material, the capillary adsorption in aperture can reinforcing material to the absorption of adsorbate.
The anode pole piece of lithium-sulphur cell positive electrode mainly is made up of positive electrode active materials, binding agent and conductive agent, by mass percentage, and positive electrode active materials 70%～85%, conductive agent 10%～25%, binding agent 5%～10%; Described positive electrode active materials is that carbon sulphur composite material or metal sulfide are active material, and carbon is carbon nano-tube, mesoporous carbon, active carbon in the described carbon sulphur composite material, and described metal sulfide is MoS
2, FeS
2, V
2S
2Or NiS; Described conductive agent is with acetylene black or superconduction carbon black; Described binding agent is the Kynoar solution of 15wt%, and solvent is the N-methyl pyrrolidone in its solution.Positive electrode active materials can produce the transiting product polysulfide in the process of battery charging and discharging.Polysulfide is easily dissolving in electrolyte, and along with electrolyte diffuses to negative pole, reacts with negative pole and corrodes negative pole, causes the performance of battery to reduce.So, in lithium-sulfur cell, add adsorption layer and can effectively adsorb the polysulfide that is dissolved in the electrolyte, prevent that it from diffusing to negative pole with electrolyte, suppress the generation of " flying the shuttle phenomenon ", improve the performance and the cycle life of lithium-sulfur cell.
The present invention adds adsorption layer and is assembled into CR2025 type button cell when the preparation lithium-sulfur cell in battery structure, concrete preparation process is as follows:
1. the preparation of anode pole piece: take by weighing the needed various materials of preparation anode pole piece, comprising: positive electrode active materials, conductive agent and binding agent, by mass percentage, positive electrode active materials 70%～85%, conductive agent 10%～25%, binding agent 5%～10%.Positive electrode active materials is carbon sulphur composite material or metal sulfide material, carbon sulphur composite material is active carbon and sulphur composite material, carbon nano-tube and sulphur composite material, mesoporous carbon and sulphur composite material or carbide derived carbon and sulphur composite material, and described metal sulfide material is MoS
2, FeS
2, V
2S
2Or NiS.Binding agent is the Kynoar solution of 15wt%, and solvent is the N-methyl pyrrolidone in its solution.The selection acetylene black of conductive agent or superconduction carbon black.Each anode constituents material is fully disperseed with absolute ethyl alcohol and grinds evenly to obtain anodal slip, the anodal slip that makes is coated in makes sheet on the nickel foam, dry anode pole piece.
2. the preparation of adsorption layer: adopt the Kynoar formulations prepared from solutions of 15wt% to become slip sorbing material, wherein the mass ratio of sorbing material and described Kynoar solution is 9: 1, solvent is the N-methyl pyrrolidone in its solution of described Kynoar, and adopting knife coating or spraying process is the adsorption layer of 5～10um at membrane surface preparation-layer thickness.
3. lithium-sulfur cell preparation: with prepared anode pole piece, adsorption layer, assemble lithium-sulfur cell with negative pole and barrier film, anodally use aluminium flake to be collector, negative pole use copper sheet be made collector.Negative pole is selected metal lithium sheet or lithium alloy for use, and described lithium alloy is Li and Si alloy, Li and Sn alloy, or Li and C alloy etc.Barrier film is selected polypropylene, polyethylene, Kynoar or polypropylene or polyethylene duplicature for use.Electrolyte is liquid, solid-state or gel-like electrolyte, liquid electrolyte is mainly selected some linear ethers or carbonates solvent for use, as ethylene carbonate methyl esters, propene carbonate, dimethyl carbonate, dioxolanes, tetraethyleneglycol dimethyl ether or oxolane etc., commonly used is two or more mixed organic solvents, as ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate mixed solvent, butyl oxide link and tetraethyleneglycol dimethyl ether mixed solvent.The electrolyte solute is lithium hexafluoro phosphate, lithium perchlorate or trifluoromethyl sulfonic acid lithium etc.
The test lithium-sulfur cell is unified to be CR2025 type button cell, and the battery charging and discharging test condition is: under the room temperature environment, and at deboost 1.2～3.0V, charging and discharging currents density 0.15mA/cm
2Condition under carry out charge-discharge test.
Description of drawings
Fig. 1 is the lithium-sulfur cell structural representation of the no adsorption layer of tradition.
Fig. 2 is the lithium-sulphur cell positive electrode structural representation that the present invention adds adsorption layer.
The interpolation that Fig. 3 embodiment 1 and Comparative Examples 1 obtain adsorption layer lithium-sulfur cell with do not add the lithium-sulfur cell cycle performance correlation curve of adsorption layer.
Among the figure: 1-collector, 2-positive pole, 3-adsorption layer, 4-porous septum, 5-negative pole.
Embodiment
Further specify preparation and performance of having added the lithium-sulfur cell lithium of adsorption layer of the present invention below by embodiment.
Positive pole plate of lithium-sulfur cell quality of the present invention percentage composition is: positive electrode active materials, conductive agent and binding agent, by mass percentage, positive electrode active materials 70%～85%, conductive agent 10%～25%, binding agent 5%～10%.
Embodiment 1
Select for use carbon nano-tube and sulphur composite material as positive electrode active materials, acetylene black is as conductive agent, the Kynoar solution of 5wt% (solution solvent is the N-methyl pyrrolidone) is as the anodal slip of adhesive preparation, and wherein the mass ratio of positive electrode active materials, conductive agent and binding agent is 80%: 15%: 5%.Then slip is coated on the nickel foam preparation in flakes, the anode pole piece that thickness is 45～55um is promptly made in oven dry.
Selecting specific area for use is 1000m
2The active carbon of/g is as the sorbing material of adsorption layer, the sorbing material active carbon is become adsorption layer in the porous septum surface preparation, porous septum selects for use the Celgard2400 film preparation to become CR2025 type button cell, wherein electrolyte is the LiPF6/EC of 1mol/L: DMC: EMC (1: 1: 1 volume ratio, EC: ethylene carbonate, DMC: dimethyl carbonate, EMC: methyl ethyl carbonate), the entire cell assembling process is all finished in glove box.
The constant current charge-discharge test result shows that the first discharge specific capacity of this battery reaches 740.4mAh/g, after 50 charge and discharge cycles, still remains on 559.8mAh/g, the results are shown in shown in Figure 3.Compare with the battery that does not add adsorption layer, the battery that has added adsorption layer has demonstrated good battery performance.
Embodiment 2
Select for use carbon nano-tube and sulphur composite material as positive electrode active materials, acetylene black is as conductive agent, the Kynoar solution of 5wt% (solution solvent is the N-methyl pyrrolidone) is as the anodal slip of adhesive preparation, wherein the mass ratio of positive electrode active materials, conductive agent and binding agent is 80%: 15%: 5%, and porous carbon microsphere prepares anode pole piece as the sorbing material of adsorption layer.Prepare anode pole piece and assembled battery by the method identical with embodiment 1.
The battery charging and discharging test result shows that the first charge-discharge specific capacity of material is 780.3mAh/g, and 50 times circulation back specific capacity also remains on 587.2mAh/g, has shown good battery performance.
Embodiment 3
(wherein the pore-size distribution of carbide derived carbon is 0.5～5nm) as positive electrode active materials to select carbide derived carbon and sulphur composite material for use, acetylene black is as conductive agent, binding agent is identical with embodiment 1, the preparation anode pole piece, the mass ratio of active material, conductive agent and binding agent is 80%: 12%: 8% in the anode pole piece.Material preparation becomes adsorption layer to mesoporous carbon as adsorption layer, prepares anode pole piece and assembled battery by the method identical with embodiment 1.
Charge-discharge test is the result show, the first charge-discharge specific capacity of material is 753.7mAh/g, and 50 times circulation back specific capacity also remains on 548.1mAh/g, has shown good battery performance.
Embodiment 4
Select for use mesoporous carbon and sulphur composite material as positive electrode active materials, acetylene black is as conductive agent, and binding agent is identical with embodiment 1, and wherein the mass ratio of positive electrode active materials, conductive agent and binding agent is 85%: 10%: 5%.Carbon molecular sieve is as adsorption layer material preparation adsorption layer, prepares anode pole piece and assembled battery by the method identical with embodiment 1.Charge-discharge test is the result show, the first charge-discharge specific capacity of material is 739.2mAh/g, and 50 times circulation back specific capacity also remains on 568.4mAh/g, has shown good battery performance.
Select for use mesoporous carbon and sulphur composite material to prepare anode pole piece as positive electrode active materials, the superconduction carbon BP 2000 is as conductive agent, binding agent is identical with embodiment 1, and the mass ratio of positive electrode active materials, conductive agent and binding agent is 80%: 12%: 8% in the anode pole piece; Material preparation becomes adsorption layer as adsorption layer to select macroporous absorbent resin Amberlite XAD-4 for use, prepares anode pole piece and assembled battery by the method identical with embodiment 1.
Charge-discharge test is the result show, the first charge-discharge specific capacity of material is 721.2mAh/g, and 50 times circulation back specific capacity also remains on 529.5mAh/g, has shown good battery performance.
Embodiment 6
Select for use mesoporous carbon and sulphur composite material as positive electrode active materials, the superconduction carbon BP 2000 is as conductive agent, binding agent is identical with embodiment 1, the preparation anode pole piece, and the mass ratio of positive electrode active materials, conductive agent and binding agent is 80%: 12%: 8% in the anode pole piece.Material preparation becomes adsorption layer as adsorption layer to select diatomite for use, prepares anode pole piece and assembled battery by the method identical with embodiment 1.
Charge-discharge test is the result show, the first charge-discharge specific capacity of material is 694.3mAh/g, and 50 times circulation back specific capacity also remains on 518.6mAh/g, has shown good battery performance.
Embodiment 7
Select for use carbon nano-tube and sulphur composite material as positive electrode active materials, the superconduction carbon BP 2000 is as conductive agent, binding agent is identical with embodiment 1, the preparation anode pole piece, and the mass ratio of positive electrode active materials, conductive agent and binding agent is 80%: 12%: 8% in the anode pole piece.Material preparation becomes adsorption layer as adsorption layer to select palygorskite for use, prepares anode pole piece and assembled battery by the method identical with embodiment 1.
Charge-discharge test is the result show, the first charge-discharge specific capacity of material is 683.5mAh/g, and 50 times circulation back specific capacity also remains on 515.0mAh/g, has shown good battery performance.
Embodiment 8
Select for use carbon nano-tube and sulphur composite material as positive electrode active materials, the superconduction carbon BP 2000 is as conductive agent, binding agent is identical with embodiment 1, the preparation anode pole piece, and the mass ratio of active material, conductive agent and binding agent is 80%: 12%: 8% in the anode pole piece.Material preparation becomes adsorption layer as adsorption layer to select sepiolite for use, prepares anode pole piece and assembled battery by the method identical with embodiment 1.
Charge-discharge test is the result show, the first charge-discharge specific capacity of material is 681.1mAh/g, and 50 times circulation back specific capacity also remains on 539.5mAh/g, has shown good battery performance.
Embodiment 9
Select FeS for use
2As positive electrode active materials, the superconduction carbon BP 2000 is as conductive agent, and binding agent is identical with embodiment 1, the preparation anode pole piece, and wherein the mass ratio of positive electrode active materials, conductive agent and binding agent is 70%: 25%: 5%.Mesoporous carbon is as adsorption layer material preparation adsorption layer, and electrolyte is selected the LiCF of 1mol/L for use
3SO
3(1: 1 volume ratio, TGM: tetraethyleneglycol dimethyl ether, DOL: dioxolanes), the anode pole piece preparation is identical with the method for embodiment 1 with the battery assembling for/TGM: DOL.
Charge-discharge test is the result show, the first charge-discharge specific capacity of material is 637.9mAh/g, and 50 times circulation back specific capacity also remains on 526.3mAh/g, has shown good battery performance.
Except selecting for use NiS, prepare anode pole piece and assembled battery by the method identical with embodiment 9 as the positive electrode active materials.Charge-discharge test is the result show, the first charge-discharge specific capacity of material is 591.2mAh/g, and 50 times circulation back specific capacity also remains on 498.7mAh/g, has shown good battery performance.
The comparative example
Referring to Fig. 1, in the cell preparation process, do not add adsorption layer.Positive electrode active materials is carbon nano-tube and sulphur composite material, select for use acetylene black as conductive agent equally, (solvent is NMP to the Kynoar solution of 5wt%, the N-methyl pyrrolidone) as the anodal slip of adhesive preparation, wherein the mass ratio of positive electrode active materials, conductive agent and binding agent is 80%: 15%: 5%.Slip is coated on the nickel foam preparation in flakes, and oven dry promptly obtains required anode pole piece, and the thickness of anode pole piece is 45～55um.Select for use the Celgard2400 film to be assembled into battery, the LiPF of electrolyte 1mol/L as the battery porous septum
6/ EC: DMC: EMC (1: 1: 1 volume ratio, EC: ethylene carbonate, DMC: dimethyl carbonate, EMC: methyl ethyl carbonate).Charge-discharge test is the result show, the first charge-discharge specific capacity of material is 616.7mAh/g, and 50 times circulation back specific capacity decays to 474.3mAh/g.
Compare with the comparative example, adopt each embodiment (having added adsorption layer in the battery structure) of the technology of the present invention, the specific capacity of battery and cycle performance have all had significant raising.The adsorption layer of the present invention in lithium-sulfur rechargeable battery is described, can stops of the migration of many lithium sulfides, suppress the generation of " flying the shuttle phenomenon ", thereby improve the performance of battery to negative pole.Lithium-sulfur cell of the present invention can be prepared into different shapes as requested, to satisfy the requirement of profile.
Claims (8)
1. lithium-sulfur cell, it comprises a positive pole, and a negative pole, a porous septum, and electrolyte, porous septum is characterized in that between positive and negative electrode it also comprises an adsorption layer, and described adsorption layer is between anode pole piece and porous septum.
2. lithium-sulfur cell according to claim 1 is characterized in that wherein the adsorption layer material is the porous adsorbing material with high-specific surface area, comprises porous carbon materials, palygorskite-sepiolite group mineral fibres, diatomite and polymeric adsorbent.
3. lithium-sulfur cell according to claim 2 is characterized in that described porous carbon materials is active carbon, carbosphere, mesoporous carbon, carbon molecular sieve or carbide derived carbon.
4. lithium-sulfur cell according to claim 1 is characterized in that the anode pole piece of described positive pole mainly is made up of positive electrode active materials, binding agent and conductive agent, by mass percentage, positive electrode active materials 70%～85%, conductive agent 10%～25%, binding agent 5%～10%; Described positive electrode active materials is that carbon sulphur composite material or metal sulfide are active material, and carbon is carbon nano-tube, mesoporous carbon, active carbon in the described carbon sulphur composite material, and described metal sulfide is FeS
2Or NiS; Described conductive agent is with acetylene black or superconduction carbon black; Described binding agent is the Kynoar solution of 15wt%, and solvent is the N-methyl pyrrolidone in its solution.
5. lithium-sulfur cell according to claim 1 is characterized in that, described porous septum is polypropylene and polyethylene duplicature.
6. lithium-sulfur cell according to claim 1, it is characterized in that, described electrolyte is nonaqueous electrolytic solution, electrolyte solvent is ethylene carbonate, dimethyl carbonate and methyl ethyl carbonate mixed solvent, perhaps be dioxolanes and tetraethyleneglycol dimethyl ether mixed solvent, the electrolyte solute is lithium hexafluoro phosphate or trifluoromethyl sulfonic acid lithium.
7. the lithium-sulfur cell of stating according to claim 1 is characterized in that, negative material is a metal lithium sheet.
8. lithium-sulfur cell according to claim 1, it is characterized in that, wherein the preparation of adsorption layer is: adopt the Kynoar formulations prepared from solutions of 15wt% to become slip sorbing material, wherein the mass ratio of sorbing material and described Kynoar solution is 9: 1, solvent is the N-methyl pyrrolidone in its solution of described Kynoar, adopts knife coating or spraying process to prepare the adsorption layer that a layer thickness is 5～10um at membrane surface.
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