CN106711497A - Lithium-sulfur battery positive pole plate - Google Patents

Lithium-sulfur battery positive pole plate Download PDF

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CN106711497A
CN106711497A CN201710135864.8A CN201710135864A CN106711497A CN 106711497 A CN106711497 A CN 106711497A CN 201710135864 A CN201710135864 A CN 201710135864A CN 106711497 A CN106711497 A CN 106711497A
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lithium
solvent
naphthalene
poly
sulfur
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CN106711497B (en
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宗铭
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Tongxiang Levi new materials Co.,Ltd.
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俞国宏
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Abstract

The invention relates to a lithium-sulfur battery positive pole plate. The lithium-sulfur battery positive pole plate is characterized in that the positive pole plate is prepared by taking a polynaphthalene/sulfur composite material as a positive pole active substance, taking a mixture of Ketjen black ECP600JD and nano carbon fibers combined at a mass ratio of 1:3 as a conductive agent, and taking a mixture system of polyvinylpyrrolidone and polyethyleneimine mixed at a volume ratio of 2:1 as an adhesive, wherein the mass ratio of the polynaphthalene/sulfur composite material, the conductive agent and the adhesive in sulfur-bearing positive pole slurry is 8:5:1.

Description

A kind of lithium-sulphur cell positive electrode piece
Technical field
The present patent application is the applying date 2016 year 02 month 05, Application No.：201610080160.0, it is entitled " a kind of The divisional application of the application for a patent for invention of the preparation method of lithium-sulfur cell ".The invention belongs to electrode material preparation field, especially relate to And a kind of lithium sulphur battery electrode material and method that lithium-sulfur cell is prepared using this kind of electrode material.
Background technology
Lithium ion battery (Lithium-ion battery, LIB), is also called lithium secondary battery, is that a kind of being recycled is filled The portable power source equipment of electricity.LIB has high-energy-density, high power density, has extended cycle life, cleans nontoxic and memory-less effect Many advantages, such as, since the nineties in last century, be commercialized for LIB by Sony, LIB has obtained rapidly and widely developing. Current LIB is own through the power supply as most of mobile electronic devices.In recent years, people had carried out deeply to LIB and had widely ground Study carefully.In LIB, negative material has very big influence to the performance of battery, and it is also to improve LIB to develop excellent negative material One of key factor of energy.Carbon material is a kind of topmost LIB negative materials, and oneself is through there is hundreds of to possess different structure at present Carbon material be used as lithium ion battery negative, these materials include native graphite, electrographite, coke, carbon fiber, interphase Carbosphere, carbon black etc..
However, there are problems in lithium-sulfur cell commercialization process, such as lithium metal unstable chemcial property is deposited when using Potential dangerous；When negative pole uses metallic lithium foil, battery is by after multiple discharge and recharge, metallic lithium foil surface easily forms branch It is brilliant.The continuous growth of dendrite causes battery capacity to decline, and dendritic growth may pierce through barrier film, causes battery short circuit, triggers peace Full problem.
Hard carbon is the pyrolytic carbon of high molecular polymer, even if being also difficult to graphitization at high temperature.The reversible capacity energy of hard carbon Higher, cycle performance is also fine.But hard carbon there is also, and electrode potential is too high, delayed (i.e. intercalation potential is less than de- lithium electricity to current potential Position) and first circulation irreversible capacity it is big the shortcomings of.
At present, most of lithium-sulfur cell all uses lithium metal as negative pole.Lithium is as negative pole in multiple charge and discharge process Being formed for a product can be caused by ten current density inequalities.Branch product can cause barrier film to penetrate, and then battery is short-circuited, and be main Potential safety hazard source.If adding Graphene in negative pole, the specific surface area of negative pole becomes big, and surface current density reduces, meanwhile, Loose Graphene provides the space of lithium deposition, so that the growth of lithium branch product is more and more difficult.Exist for cathode of lithium Problem, improvement and study less that researcher is carried out.Summing up mainly includes two aspects：One is from electrolyte addition Agent is modified, by adding different additives, such as LiNO3With PEO etc., promote cathode of lithium surface fast in charge and discharge process Speed forms more stable SEI films, it would be desirable to suppresses Li dendrite and improves cycle performance.But additive is in charge and discharge process Gradually it is consumed, influences the stability and continuity of battery.Two are started with from the preparation technology of lithium electrode, are closed by using lithiumation Thing coats lithium powder or electrodeposit metals lithium, and lithium paper tinsel surface increases the methods such as protective layer, improves cycle efficieny and cycle life, But operating process is also complex.
The content of the invention
In order to solve problems of the prior art, it is an object of the invention to provide one kind is by stable state lithium powder and special matches somebody with somebody Than the cathode size that carbon material is prepared from, and the lithium-sulfur cell being prepared from by the slurry, which solve in the prior art Using the material strips such as hard carbon come technological deficiency and solve cathode of lithium battery it is improved present in stability and continuity The technical problem such as difference and complex operation.
A kind of preparation method of lithium-sulfur cell, comprises the following steps：
The preparation of step 1, positive plate：With poly- naphthalene/sulphur composite as positive active material, Ketjen black ECP600JD and nano-sized carbon Fiber is 1 according to mass ratio:3 mixtures for combining are conductive agent, and polyvinylpyrrolidone and polyethyleneimine are according to body Product is than being 2:1 mixed system for mixing is binding agent；Poly- naphthalene/sulphur composite in the anode sizing agent of sulfur-bearing, conductive agent It is 8 with the mass ratio of binding agent:5:1；Mixture binding agent is dissolved in by ethylene carbonate（EC）, ethylene methacrylic ester（MA）With three Fluoropropylene carbonate（TFPC）It is 7 according to volume ratio:7:Solution is made in 1 solvent for mixing；Wherein, according to quality meter Calculate, solvent is weighed according to the ratio that solids content is 30%, solid includes poly- naphthalene/sulphur composite and conductive agent；Again by poly- naphthalene/ After sulphur composite is well mixed in mass ratio with conductive agent, pour into the solvent for having dissolved binding agent, be fabricated to anode sizing agent；
Then the slurry that will be obtained is uniformly coated in foamed nickel current collector.It is placed in again in vacuum drying chamber and dries, removes solvent And moisture, the temperature in vacuum drying chamber is 55 DEG C, and drying time is 9h, is struck off the slurry of foam nickel surface with blade dry Only, then positive plate flatten, then positive plate is placed in vacuum drying chamber and is dried again；
It is prepared by step 2, negative plate：Stable state lithium powder and carbon material are weighed according to mass ratio, with ethylene carbonate（EC）, methyl second Alkene ester（MA）With three fluoropropylene carbonates（TFPC）It is 7 according to volume ratio:7:1 mixture for mixing is solvent.Wherein, According to Mass Calculation, solvent is weighed according to the ratio that solids content is 30%, solid includes stable state lithium powder and carbon material；First carbon Material is dissolved in solvent, and then stable state lithium powder is poured into above-mentioned solution, is applied in foamed nickel current collector after being well mixed So as to obtain negative plate；Negative plate is placed on heating plate and is heated so that solvent volatilizees；Then negative plate is flattened stand-by；Its In, the mass ratio of stable state lithium powder and carbon material is 7-10:3-8；The temperature heated on heating plate is 70 DEG C, and the heat time is 8h；
Step 3, battery assembling：Lithium-sulfur cell is assembled into using negative plate obtained in positive plate obtained in step 1 and step 2.
Further, described in step 1 with blade by the slurry scraped clean of foam nickel surface, the operation that positive plate is flattened Completed in vacuum glove box.
Further, negative plate is placed on heating plate in step 2 and is heated so that solvent volatilization, then flattens negative plate and treat Operation is completion in vacuum glove box.
Further, the stable state lithium powder described in step 2 is made up of dropping liquid emulsifying technology (DET), a diameter of 50 μm -70 of lithium powder μm。
A kind of lithium-sulfur cell negative material, it is characterised in that including：In terms of mass fraction, by following feedstock composition group Into：7-10 parts of stable state lithium powder, 3-8 parts of carbon material and solvent.
Further, described stable state lithium powder is made up of dropping liquid emulsifying technology (DET), a diameter of 50 μm -70 μm of lithium powder.
Further, described carbon material is that vertical array column-shaped CNT (VACNT) and mesoporous carbon are 10 according to mass ratio： 1 mixture for mixing.
Further, the solvent is ethylene carbonate（EC）, ethylene methacrylic ester（MA）With three fluoropropylene carbonates （TFPC）It is 7 according to volume ratio:7:1 mixed solvent for mixing.
A kind of preparation method of lithium-sulfur cell, using lithium-sulfur cell negative material as described above as negative pole, its feature It is to comprise the following steps：
（1）The anode sizing agent of sulfur-bearing is coated in collector and is made positive plate；
（2）Stable state lithium powder and carbon material are weighed according to mass ratio, with ethylene carbonate（EC）, ethylene methacrylic ester（MA）And trifluoro For propene carbonate（TFPC）It is 7 according to volume ratio:7:1 mixture for mixing is solvent；First carbon material dissolving In the solvent, then stable state lithium powder is poured into above-mentioned solution, be applied on collector so as to be born after being well mixed Pole piece；Negative plate is placed on heating plate and is heated so that solvent volatilizees；Then negative plate is flattened stand-by；
（3）Positive pole, negative pole, barrier film are assembled into button cell.
Further, step（1）Described in the anode sizing agent of sulfur-bearing include：Poly- naphthalene/sulphur composite, conductive agent, bonding Agent and solvent；Described conductive agent is 1 according to mass ratio by Ketjen black ECP600JD and carbon nano-fiber:3 combine, described Binding agent by polyvinylpyrrolidone and polyethyleneimine according to volume ratio be 2:1 mixes；The solvent is by ethylene Alkene ester（EC）, ethylene methacrylic ester（MA）With three fluoropropylene carbonates（TFPC）It is 7 according to volume ratio:7:1 mixes；First will In the mixed solvent that binding agent is dissolved in, then after poly- naphthalene/sulphur composite is well mixed in mass ratio with conductive agent, pour into Dissolve in the solvent of binding agent, be fabricated to anode sizing agent, then by anode sizing agent uniform application on a current collector, be made positive pole Piece.
Further, the positive plate need to be heated in vacuum drying chamber and remove moisture removal and solvent, then strike off its surface And pressing；Temperature in described vacuum drying chamber is 55 DEG C, and drying time is 9h.
Further, the mass ratio of the poly- naphthalene in the anode sizing agent of described sulfur-bearing/sulphur composite, conductive agent and binding agent It is 8:5:1.
Further, step（2）Described in negative plate need to 40 DEG C -70 DEG C heating 8h-11h to remove solvent, then flatten It is stand-by.
Further, step（2）With（3）In operation in the vacuum glove box full of argon gas completion.
The lithium-sulfur cell negative material and lithium-sulfur cell that the present invention is prepared have the advantages that：
（1）The negative pole that the lithium-sulfur cell negative material that the present invention is prepared is made by the carbon material of stable state lithium powder and specific proportioning Compared with common lithium foil electrode, specific surface area is bigger, and porosity is higher, more complete with electrolyte contacts, so that effectively discharge face Product is bigger, and impedance is smaller, and can effectively suppress the growth of Li dendrite, can show preferable cycle performance and high rate performance.
（2）The lithium-sulfur cell negative material that the present invention is prepared is made up of the carbon material of stable state lithium powder and specific proportioning, The effective volume taken into account of a large amount of CNTs for wherein using serves the effect of carbon material and the effect of binding agent, effectively keeps away Exempt from the use of adhesive, the cost for cleverly reducing reduces processing step, it is close to ten actual energies for improving lithium-sulfur cell Degree also has important meaning.
（3）Had using vertical array column-shaped CNT (VACNT) in the lithium-sulfur cell negative material that the present invention is prepared There is good orientation, with collector can form good contact and form efficiently and directionally conducting matrix grain, effectively improve lithium-sulfur cell Negative material middle skeleton electric conductivity.Its structural advantage for fully combining mesoporous carbon again, highly ordered mesosize pores carbon has specific surface Product is big, uniform pore diameter, pore volume is very high, loose structure and the high conductivity of being mutually related the features such as.Fully profit of the invention With the advantage of both structure, can effectively weaken shuttle effect and the dendritic growth in continuous charge and discharge process, compare conventional electrodes Show more preferable cycle performance and high rate performance.
（4）In terms of the conductive additive of positive pole, the present invention addition Ketjen black ECP600JD and carbon nano-fiber, Hou Zheke Three-dimensional conductive network is formed, the remote conductive ability in pole piece can be increased, be difficult to be permitted the product of formation in discharge process again It is completely covered, so as to improve the surface texture of pole piece;The former using Ketjen black ECP600JD rich space pore passage structure and Good adsorption properties, can also improve the cycle performance of lithium-sulfur cell.
（5）Positive active material of the invention have selected poly- naphthalene/sulphur composite, and poly- naphthalene is used for having one in lithium-sulfur cell Determine advantage:(1) poly- naphthalene is conducting polymer, big in structure, and n keys make it easier to conduction, can be obviously improved the conduction of sulfur electrode Property;(2) poly- naphthalene has the layer structure of similar graphite, and its structure is more easy to be closely connected with elemental sulfur, can suppress its electrode anti- Answer the dissolving in the electrolytic solution of many lithium sulfides of product;(3) poly- naphthalene has certain capacity as electrode material, can be with sulfur electrode Produce synergy.
（6）The present invention has also especially selected the mixed system of polyvinylpyrrolidone and polyethyleneimine in positive electrode As binding agent, so as to the loose structure with strong holding sulphur positive pole in cyclic process.
（7）The present invention has selected three kinds of mixed systems of material solvent the most, and by experiment, the solvent can preferably keep The architectural feature and advantage of the raw material of various pole pieces, same ethylene carbonate（EC）, ethylene methacrylic ester（MA）Can obtain good Good low temperature properties, and plus three a small amount of fluoropropylene carbonates（TFPC）Preferable discharge capacity and circulation longevity can be obtained Life.The selection of three kinds of solvents takes into account the factor in terms of the optimum combination performance and cost that consider solvent so that final to prepare The product for obtaining has the quality of more preferable stability and Geng Gao.
Specific embodiment
Embodiment one：
The preparation of positive plate：With poly- naphthalene/sulphur composite as positive active material, Ketjen black ECP600JD and carbon nano-fiber press It is 1 according to mass ratio:3 mixtures for combining are conductive agent, and polyvinylpyrrolidone and polyethyleneimine are according to volume ratio 2:1 mixed system for mixing is binding agent.
The mass ratio of poly- naphthalene in the anode sizing agent of sulfur-bearing/sulphur composite, conductive agent and binding agent is 8:5:1.Mixed Fit binding agent is dissolved in by ethylene carbonate（EC）, ethylene methacrylic ester（MA）With three fluoropropylene carbonates（TFPC）According to volume Than being 7:7:Solution is made in 1 solvent for mixing.Wherein, according to Mass Calculation, claim according to the ratio that solids content is 30% Solvent is taken, solid includes poly- naphthalene/sulphur composite and conductive agent.Poly- naphthalene/sulphur composite and conductive agent are mixed in mass ratio again After closing uniformly, pour into the solvent for having dissolved binding agent, be fabricated to anode sizing agent.
Then the slurry that will be obtained is uniformly coated in foamed nickel current collector.It is placed in again in vacuum drying chamber and dries, removes Solvent and moisture, the temperature in vacuum drying chamber is 55 DEG C, and drying time is 9h, is struck off the slurry of foam nickel surface with blade Totally, then with certain pressure positive plate is flattened.Then positive plate is placed in vacuum drying chamber and is dried again.Operate above equal Completed in vacuum glove box.
It is prepared by negative plate：Stable state lithium powder and carbon material are weighed according to mass ratio, with ethylene carbonate（EC）, ethylene methacrylic Ester（MA）With three fluoropropylene carbonates（TFPC）It is 7 according to volume ratio:7:1 mixture for mixing is solvent.Wherein, press According to Mass Calculation, solvent is weighed according to the ratio that solids content is 30%, solid includes trustworthy state lithium powder and carbon material.
First carbon material is dissolved in solvent, then stable state lithium powder is poured into above-mentioned solution, be applied to after being well mixed So as to obtain negative plate in foamed nickel current collector；Negative plate is placed on heating plate and is heated so that solvent volatilizees；Then negative pole Piece flattens stand-by；Wherein, the mass ratio of stable state lithium powder and carbon material is 10:8；The temperature heated on heating plate is 70 DEG C, heating Time is 8h.Operation above is completed in vacuum glove box.
Preparation method on poly- naphthalene/sulphur composite：Take appropriate poly- naphthalene to be scattered in deionized water, ultrasonic disperse, plus Enter a certain amount of Na2S203.5H2Ultrasonic disperse again after 0;To the hydrochloric acid solution that 1 appropriate mol/L is slowly added dropwise in mixture, Being 7 to above-mentioned solution ph；Continue suction filtration after stirring reaction, sample is placed in vacuum drying chamber and is dried, that is, gathered Naphthalene/sulphur composite.
Battery is assembled and test：Button battery is assembled in the glove box full of argon gas.With above-mentioned negative plate as negative pole, Using Celgard2400 barrier films and 2025 type button batteries.Electrolyte is dissolved in DOL for 1M LiClO4,0.15M LiNO3： DME（Volume ratio 1：1）.Battery is placed in blue electrical measurement test system（CT2001A）Carry out constant current test.Charging/discharging voltage scope is 1.5- 3.0V, test temperature is room temperature.
Embodiment two：
Compared with embodiment one, in negative plate preparation process, the mass ratio for changing stable state lithium powder and carbon material is embodiment two 7:3, the temperature heated on heating plate is 40 DEG C, and the heat time is 11h.Remaining operation and explanation are with embodiment one.
Embodiment three：
Compared with embodiment one, in negative plate preparation process, the mass ratio for changing stable state lithium powder and carbon material is embodiment two 6:5, the temperature heated on heating plate is 60 DEG C, and the heat time is 9h.Remaining operation and explanation are with embodiment one.
Compared to common lithium foil electrode, when the negative pole of embodiment one, two and three is using stable state lithium powder and mixing carbon material, Lithium-sulfur cell of the invention can show more preferable first charge-discharge specific capacity, while capability retention exists after 100 circulations More than 95.8%.
The button cell of each embodiment is AC impedance contrast experiment after standing 24 hours.Experimental result shows, works as implementation After example one, two and three is using stable state lithium powder and mixing carbon material, compared to common lithium foil electrode, the resistance of lithium-sulfur cell of the invention It is anti-to greatly reduce, reason be stable state lithium powder specific surface area is big and electrolyte contacts completely, faster electronics can be shown and passed Pass and shift.
Meanwhile, the lithium-sulfur cell negative material that the present invention is prepared is by stable state lithium powder and the carbon material group of specific proportioning Into, wherein the volume that a large amount of CNTs for using effectively are taken into account serves the effect of carbon material and the effect of binding agent, effectively The use for avoiding adhesive, the cost for cleverly reducing reduces processing step, to the ten actual energy for improving lithium-sulfur cells Metric density also has important meaning.
（3）Had using vertical array column-shaped CNT (VACNT) in the lithium-sulfur cell negative material that the present invention is prepared There is good orientation, with collector can form good contact and form efficiently and directionally conducting matrix grain, effectively improve lithium-sulfur cell Negative material middle skeleton electric conductivity.Its structural advantage for fully combining mesoporous carbon again, highly ordered mesosize pores carbon has specific surface Product is big, uniform pore diameter, pore volume is very high, loose structure and the high conductivity of being mutually related the features such as.Fully profit of the invention With the advantage of both structure, can effectively weaken shuttle effect and the dendritic growth in continuous charge and discharge process, compare conventional electrodes Show more preferable cycle performance and high rate performance.
（4）In terms of the conductive additive of positive pole, the present invention addition Ketjen black ECP600JD and carbon nano-fiber, Hou Zheke Three-dimensional conductive network is formed, the remote conductive ability in pole piece can be increased, be difficult to be permitted the product of formation in discharge process again It is completely covered, so as to improve the surface texture of pole piece;The former using Ketjen black ECP600JD rich space pore passage structure and Good adsorption properties, can also improve the cycle performance of lithium-sulfur cell.
（5）Positive active material of the invention have selected poly- naphthalene/sulphur composite, and poly- naphthalene is used for having one in lithium-sulfur cell Determine advantage:(1) poly- naphthalene is conducting polymer, big in structure, and n keys make it easier to conduction, can be obviously improved the conduction of sulfur electrode Property;(2) poly- naphthalene has the layer structure of similar graphite, and its structure is more easy to be closely connected with elemental sulfur, can suppress its electrode anti- Answer the dissolving in the electrolytic solution of many lithium sulfides of product;(3) poly- naphthalene has certain capacity as electrode material, can be with sulfur electrode Produce synergy.
（6）The present invention has also especially selected the mixed system of polyvinylpyrrolidone and polyethyleneimine in positive electrode As binding agent, so as to the loose structure with strong holding sulphur positive pole in cyclic process.
（7）The present invention has selected three kinds of mixed systems of material solvent the most, and by experiment, the solvent can preferably keep The architectural feature and advantage of the raw material of various pole pieces, same ethylene carbonate（EC）, ethylene methacrylic ester（MA）Can obtain good Good low temperature properties, and plus three a small amount of fluoropropylene carbonates（TFPC）Preferable discharge capacity and circulation longevity can be obtained Life.The selection of three kinds of solvents takes into account the factor in terms of the optimum combination performance and cost that consider solvent so that final to prepare The product for obtaining has the quality of more preferable stability and Geng Gao.
Above example has been shown and described general principle of the invention, principal character and advantages of the present invention.The industry Technical staff it should be appreciated that the present invention is not limited to the above embodiments, described in above-described embodiment and specification simply Principle of the invention is illustrated, rather than the scope of the present invention is limited by any way, without departing from the scope of the invention, Various changes and modifications of the present invention are possible, and these changes and improvements are both fallen within claimed scope.

Claims (3)

1. a kind of lithium-sulphur cell positive electrode piece, the preparation of positive plate is comprised the following steps：
Step 1, with poly- naphthalene/sulphur composite as positive active material, Ketjen black ECP600JD and carbon nano-fiber be according to quality Than being 1:3 mixtures for combining are conductive agent, and polyvinylpyrrolidone and polyethyleneimine are 2 according to volume ratio:1 mixing Mixed system be binding agent；The quality of poly- naphthalene in the anode sizing agent of sulfur-bearing/sulphur composite, conductive agent and binding agent Than being 8:5:1；Mixture binding agent is dissolved in by ethylene carbonate（EC）, ethylene methacrylic ester（MA）With three fluoropropylene carbonates （TFPC）It is 7 according to volume ratio:7:Solution is made in 1 solvent for mixing；Wherein, according to Mass Calculation, contain according to solid The ratio measured as 30% weighs solvent, and solid includes poly- naphthalene/sulphur composite and conductive agent；Again by poly- naphthalene/sulphur composite with lead After electric agent is well mixed in mass ratio, pour into the solvent for having dissolved binding agent, be fabricated to anode sizing agent；
Step 2 and then the slurry that will be obtained are uniformly coated in foamed nickel current collector；
Step 3, it is placed in again in vacuum drying chamber and dries, remove solvent and moisture, temperature in vacuum drying chamber is 55 DEG C, is dried Time is 9h, with blade by the slurry scraped clean of foam nickel surface, then positive plate is flattened, and positive plate is then placed in vacuum Dried again in drying box.
2. the preparation method of lithium-sulfur cell according to claim 1, it is characterised in that：Stable state lithium powder described in step 1 by Dropping liquid emulsifying technology (DET) is made, a diameter of 50 μm -70 μm of lithium powder.
3. the preparation method of lithium-sulfur cell according to claim 1, it is characterised in that：With blade by foam in the step 3 The slurry scraped clean of nickel surface, completes the operation that positive plate is flattened in vacuum glove box.
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