CN105529446A - Lithium-sulfur battery composite positive electrode material and preparation method and application therefor - Google Patents
Lithium-sulfur battery composite positive electrode material and preparation method and application therefor Download PDFInfo
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Abstract
The invention discloses a lithium-sulfur battery composite positive electrode material and a preparation method and an application therefor. The composite positive electrode material is compounded by raw materials including elementary substance sulfur, a conductive carbon material and a lithium-containing transitional metal oxide; the preparation method comprises the steps of stirring and mixing an organic solution dissolved with the elementary substance sulfur, or a solution capable of generating the elementary substance sulfur through reaction, with a water solution dispersed with the conductive carbon material and the lithium-containing transitional metal oxide, enabling solvent to be volatilized, and performing thermal treatment on the mixture at a high temperature to obtain the lithium-sulfur battery composite positive electrode material. The prepared composite positive electrode material is high in conductivity, rich in lithium source, and capable of stabilizing and defining polysulfide within a positive electrode region and improving the utilization rate of the active substance sulfur; the composite positive electrode material is used for preparing the lithium-sulfur battery positive electrode, and the specific discharge capacity of the lithium-sulfur battery can be greatly improved and the cycling performance stability of the battery can be enhanced; and in addition, the preparation method for the composite positive electrode material is simple, mild in process conditions, low in cost and capable of satisfying industrial production requirements.
Description
Technical field
The present invention relates to a kind of lithium-sulfur battery composite anode material and its preparation method and application, in particular to a kind of elemental sulfur, conductive carbon material and lithium-containing transition metal oxide trielement composite material, and the application in the high specific discharge capacity of preparation, stable cycle performance lithium-sulphur cell positive electrode, belong to lithium-sulfur cell technical field.
Background technology
Along with the fast development of new forms of energy industry, lithium ion battery has had at portable electronics, electric automobile, extensive energy storage and military power supply to be applied widely.Especially the energetically support of country to new-energy automobile recently, the further fast development having promoted lithium electrical travelling industry, this also has higher requirement to the energy density of lithium ion battery, and the restrictive factor that the low specific capacity of the positive electrode of conventional lithium ion battery has become it maximum.The positive electrode elemental sulfur of lithium-sulfur cell is with its high theoretical specific capacity 1675mAh/g, and the features such as specific energy 2600Wh/g and low price, aboundresources, environmental friendliness, make its most wish to become follow-on electrokinetic cell.But research finds that sulphur exists a lot of defect as positive electrode: sulphur and discharging product lithium sulfide thereof are all electronic body, and conductivity only has 5 × 10
-30s/cm, causes the polarization phenomena that battery is serious in charge and discharge process; The polysulfide produced in discharge process can be dissolved in organic electrolyte, effect of shuttling back and forth, and causes the loss of active material, capacity rapid decay; In addition in positive pole without lithium source, sulphur not can embed the crystal structure of lithium ion, is unfavorable for lithium ion diffusion in the electrodes, very easily produces electrode polarization.These defects all badly influence cycle life, the capacity performance of lithium-sulfur cell and commercially produce.
Summary of the invention
There is capacity for lithium-sulfur cell of the prior art and play low, the poor problem of cycle performance, first object of the present invention is to provide one to conduct electricity very well, be rich in lithium source, and positive pole zone can be strapped in by stable for polysulfide, improve the lithium-sulfur battery composite anode material of active material utilization efficiency.
Second object of the present invention is to provide a kind of simple to operate, process conditions are gentle, low cost prepares described lithium-sulfur battery composite anode material method.
3rd object of the present invention is the application being to provide a kind of described composite positive pole, and described composite positive pole, for the preparation of lithium-sulphur cell positive electrode, can significantly improve the specific discharge capacity of lithium-sulfur cell, improves the stable cycle performance of battery.
In order to realize above-mentioned technical purpose, the invention provides a kind of lithium-sulfur battery composite anode material, this composite positive pole is composited by the raw material comprising elemental sulfur, conductive carbon material and lithium-containing transition metal oxide.
Preferred scheme, lithium-sulfur battery composite anode material is made up of following mass parts raw material components: elemental sulfur 50 ~ 80 parts; Conductive carbon material 5 ~ 25 parts; Lithium-containing transition metal oxide 5 ~ 25 parts.
More preferably scheme, conductive carbon material is at least one in section's qin carbon black, SuperP, acetylene black, Graphene, carbon nano-tube, carbon nano-fiber.
More preferably scheme is Li containing lithium transiens metal oxide
4ti
5o
12, LiFePO
4, LiCoO
2, LiNiO
2, LiMnO
2, LiMn
2o
4, LiNi
xco
ymn
zo
2, nLi
2mO
3(1-n) LiMO
2in at least one, wherein M is Ni, Co, Fe or Ni
1/2mn
1/2.
More preferably scheme, elemental sulfur is nano elemental sulfur.Elemental sulfur of the present invention is that sublimed sulfur can directly be bought, or is the nano elemental sulfur that sodium thiosulfate or vulcanized sodium pass through liquid phase method fabricated in situ.
Present invention also offers a kind of method preparing described lithium-sulfur battery composite anode material, the method comprises scheme a, scheme b or scheme c:
Scheme a: after the organic solution being dissolved with elemental sulfur and the aqueous solution being dispersed with conductive carbon material and lithium-containing transition metal oxide are uniformly mixed, solvent flashing, gained mixture is placed in heat treatment at 130 ~ 200 DEG C of temperature, to obtain final product;
Scheme b: after the solution containing sodium thiosulfate and polyvinylpyrrolidone is uniformly mixed with the aqueous solution being dispersed with conductive carbon material and lithium-containing transition metal oxide, continuing under the condition stirred, add hydrochloric acid reaction, after having reacted, solvent flashing, gained mixture is placed in heat treatment at 130 ~ 200 DEG C of temperature, to obtain final product;
Scheme c: after the solution of Containing Sulfur sodium and sodium sulfite and the aqueous solution being dispersed with conductive carbon material and lithium-containing transition metal oxide are uniformly mixed, continuing under the condition stirred, add sulfuric acid reaction, after having reacted, solvent flashing, gained mixture is placed in heat treatment at 130 ~ 200 DEG C of temperature, to obtain final product.
Preferred scheme, in scheme b, the mass ratio of sodium thiosulfate and polyvinylpyrrolidone is 20 ~ 100:1.
Preferred scheme, in scheme b, the mol ratio of sodium thiosulfate and hydrochloric acid is 1:2 ~ 3.
Preferred scheme, in scheme b, the reaction time is 1 ~ 3h.
Preferred scheme, in scheme c, the mol ratio of vulcanized sodium, sodium sulfite and sulfuric acid is 2:1:3.
Preferred scheme, in scheme c, the reaction time is 1 ~ 3h.
Preferred scheme, the time be uniformly mixed in scheme a, scheme b or scheme c is 10h ~ 30h, stirs the long enough time, each raw material is fully mixed.
Preferred scheme, in scheme a, scheme b or scheme c, solvent flashing realizes under 25 DEG C ~ 60 DEG C temperature conditions.
Preferred scheme, in scheme a, scheme b or scheme c, heat treatment time is 8h ~ 20h.
The organic solution being dissolved with elemental sulfur of the present invention, the solvent that organic solution adopts is that volatility is good, can dissolve the solvent of elemental sulfur, as carbon disulfide, alcohol, acetone, toluene, benzene, chloroform, tetrachloroethanes or amine reagent etc.Amine reagent is as ethylenediamine.
Technical scheme of the present invention, by required material quality in scheme a, elemental sulfur is dissolved in the organic solution that organic solvent obtains being dissolved with elemental sulfur, conductive carbon material and lithium-containing transition metal oxide are added to the water, after being uniformly mixed, obtain the aqueous solution being dispersed with conductive carbon material and lithium-containing transition metal oxide, then by organic solution and the aqueous solution 0.2 ~ 3:1 mixing by volume.
Present invention also offers the application of described lithium-sulfur battery composite anode material, is lithium-sulfur battery composite anode material is applied to the positive pole preparing lithium-sulfur cell.
Preferred scheme, after described lithium-sulfur battery composite anode material and conductive carbon material and binding agent mechanical mixture, mills, then adds 1-METHYLPYRROLIDONE wet-milling, be modulated into pureed slurry, be coated on aluminium foil, dries, obtains positive pole.
More preferably scheme, the mass ratio of lithium-sulfur battery composite anode material and conductive carbon material and binding agent is 65 ~ 75:15 ~ 25:10; The mass ratio most preferably being lithium-sulfur battery composite anode material and SuperP conductive carbon material and polyacrylic acid binding agent is 70:20:10.
The preparation method of lithium-sulphur cell positive electrode of the present invention: be lithium-sulfur battery composite anode material, SuperP with polyacrylic acid in mass ratio for 7:2:1 mixes, mechanical lapping 30 minutes, add 1-METHYLPYRROLIDONE wet-milling 5 minutes, be coated in after being modulated into muddy on aluminium foil, the baking oven putting into 50 DEG C is dry, obtains the anode pole piece of lithium-sulfur cell; The thickness of the anode pole piece of preparation is 100 ~ 200 μm.
The lithium transiens metal oxide that contains of the present invention (comprises Li
4ti
5o
12, LiFePO
4, LiCoO
2, LiNiO
2, LiMnO
2, LiMn
2o
4, LiNi
xco
ymn
zo
2, nLi
2mO
3(1-n) LiMO
2deng), conductive carbon material (comprising section's qin carbon black, SuperP, acetylene black, Graphene, carbon nano-tube, carbon nano-fiber etc.) is all commercially available conventional dose.
Hinge structure, the beneficial effect that technical scheme of the present invention is brought:
1, technical scheme of the present invention introduces lithium transition-metal oxide first in sulphur carbon composite anode material; Lithium transition-metal oxide provides sufficient lithium source for positive pole on the one hand, is conducive to the fast reaction of sulphur and lithium in discharge process, effectively reduces electrode polarization; On the other hand for sulphur provides loading frame, and its metallic site shows lewis acidity, has good chemisorption, thus polysulfide is strapped in positive pole zone effectively to the polysulfide of lewis base, and Absorbable organic halogens circulates.
2, the lithium-sulfur battery composite anode material proposed in technical scheme of the present invention is rich in lithium source, conducts electricity very well, and can be strapped in positive pole zone by stable for polysulfide, improves the utilance of active material sulphur.
3, the method preparing lithium-sulfur battery composite anode material proposed in technical scheme of the present invention, simple to operate, process conditions are gentle, are adapted to suitability for industrialized production.
4, in technical scheme of the present invention, the preparation of lithium-sulfur battery composite anode material adopts the mixing of solution form, solvent evaporates load, achieve sulfur molecule, fully mixing and uniform load between conductive carbon material with lithium-containing transition metal oxide, on this basis in conjunction with high-temperature process, ensure that sulphur distributes in the composite uniformly, with fully contacting of lithium-containing transition metal oxide and active carbon material; Effectively improve electron conduction and the stability of positive electrode.
5, in technical scheme of the present invention, the preparation of lithium-sulfur battery composite anode material can adopt the method for in-situ preparation nano elemental sulfur, the nano elemental sulfur of generation and conductive carbon material and lithium-containing transition metal oxide are carried out In-situ reaction, make nano-sulfur load evenly, nano-sulfur has better electro-chemical activity.
6, composite positive pole of the present invention is for the preparation of lithium-sulphur cell positive electrode, can significantly improve the specific discharge capacity of lithium-sulfur cell, improves the stable cycle performance of battery.
Accompanying drawing explanation
[Fig. 1] be embodiment 1 80 DEG C, anode composite/copolymer solid electrolyte/lithium is assembled into the charging and discharging curve of lithium-sulfur cell under 0.1C condition.
[Fig. 2] be embodiment 1 60 DEG C, anode composite/copolymer solid electrolyte/lithium is assembled into the charging and discharging curve of lithium-sulfur cell under 0.1C condition.
Embodiment
Following examples are intended to further illustrate the present invention, instead of the restriction to the claims in the present invention protection range.
Embodiment 1
Preparation component sublimed sulfur, SuperP, Li
4ti
5o
12composite positive pole, concrete preparation technology is as follows:
Prepare composite material: be first sublimed sulfur: SuperP:Li according to mass ratio
4ti
5o
12=7:1.5:1.5, the sublimed sulfur adding 0.7g is respectively dissolved in the toluene of 30mL, SuperP and 0.15gLi of 0.15g
4ti
5o
12be mixed in the ultra-pure water of 70mL, mixed by toluene with ultra-pure water, 400r/min stirs 12h, at 50 DEG C, solvent evaporates is complete, with a large amount of milli-Q water surplus materials, and under 50 DEG C of conditions vacuumize 24h, obtain black powder.By black powder heat treatment 12h under 155 DEG C of conditions in sealing tube furnace, and a straight-through argon gas is protected, and is elevated sulphur/SuperP/Li
4ti
5o
12composite material.Prepared sublimed sulfur/SuperP/Li
4ti
5o
12in composite material, the quality of sulphur accounts for 65% of gross mass.
Prepare anode pole piece: take sublimed sulfur/SuperP/Li
4ti
5o
12composite material 0.21g, SuperP0.06g, polyacrylic acid (PAA) 0.03g, be placed in mortar grinding 30 minutes, then appropriate 1-METHYLPYRROLIDONE (NMP) is added, wet-milling 5 minutes, be coated in after being modulated into muddy and used on the aluminium foil of alcohol washes, dry in the baking oven of 50 DEG C, solvent flashing 12h, obtains the anode pole piece of lithium-sulfur cell.
Anode pole piece/PEO base polymer electrolyte/lithium sheet is utilized by the anode pole piece of prepared lithium-sulfur cell to be assembled into all solid lithium sulphur button cell, at 80 DEG C, testing first circle specific discharge capacity under 0.1C is 1420mAh/g, and after circulation 10 circle, specific discharge capacity is 1527mAh/g, and efficiency is 99.3%.The test of 0.1C rate charge-discharge is carried out under 60 DEG C of conditions.First circle specific discharge capacity is 1123mAh/g, and after circulation 10 circle, specific discharge capacity is 1079mAh/g, and efficiency is 99.5%.Concrete loop test data as shown in Figure 1, 2.
Embodiment 2
Prepare and material proportion in embodiment 1, positive pole plate of lithium-sulfur cell that thickness is identical, be assembled into all solid lithium sulphur button cell, the test of 1C rate charge-discharge is carried out under 80 DEG C of conditions, first discharge specific capacity is 727mAh/g, after circulation 20 circle, specific discharge capacity is 710mAh/g, and efficiency is 99.8%.Different multiplying charge-discharge test is carried out under 80 DEG C of conditions, first circle 0.2C specific discharge capacity is 1328mAh/g, after circulation 5 circle, under 0.5C, specific discharge capacity is 794.5mAh/g, after circulation 10 circle, under 1C, specific discharge capacity is 708mAh/g, after circulation 15 circle, under 2C, specific discharge capacity is 535mAh/g, when multiplying power progressively gets back to 0.2C, after circulation 20 circle, specific discharge capacity is 835mAh/g, and efficiency is 98.3%.
Embodiment 3
Preparation component sublimed sulfur, carbon nano-tube, LiFePO
4composite positive pole, concrete preparation technology is as follows: prepare composite material: be first sublimed sulfur according to mass ratio: carbon nano-tube: LiFePO
4=8:1:1, the sublimed sulfur adding 0.8g is respectively dissolved in the carbon disulfide of 20mL, SuperP and 0.1gLiFePO of 0.1g
4be mixed in the ultra-pure water of 80mL, carbon disulfide mixed with ultra-pure water, the stirring 15h of 500r/min, at 30 DEG C, solvent evaporates is complete, with a large amount of milli-Q water surplus materials, and under 50 DEG C of conditions vacuumize 24h, obtain black powder.By black powder heat treatment 20h under 155 DEG C of conditions in sealing tube furnace, and a straight-through argon gas is protected, and is elevated sulphur/carbon nano-tube/LiFePO
4composite material.Prepared sublimed sulfur/carbon nano-tube/LiFePO
4the quality of middle sulphur accounts for 73% of gross mass.
Prepare anode pole piece: take sublimed sulfur/carbon nano-tube/LiFePO
4composite material 0.21g, SuperP0.06g, polyacrylic acid (PAA) 0.03g, be placed in mortar grinding 30 minutes, then appropriate 1-METHYLPYRROLIDONE (NMP) is added, wet-milling 5 minutes, be coated in after being modulated into muddy and used on the aluminium foil of alcohol washes, dry in the baking oven of 50 DEG C, solvent flashing 12h, obtains the anode pole piece of lithium-sulfur cell.
Anode pole piece/lithium-sulfur cell ethers electrolyte/lithium sheet is utilized by the anode pole piece of prepared lithium-sulfur cell to be assembled into button cell, in room temperature, testing first circle specific discharge capacity under 0.2C is 1250mAh/g, and after circulation 100 circle, specific discharge capacity is 759mAh/g, and efficiency is 99.4%.Carry out the test of 0.1C rate charge-discharge at ambient temperature.First circle specific discharge capacity is 1380mAh/g, and after circulation 100 circle, specific discharge capacity is 946mAh/g, and efficiency is 99.7%.
Embodiment 4
Prepare and material proportion in embodiment 3, positive pole plate of lithium-sulfur cell that thickness is identical, be assembled into button cell, carry out the test of 1C rate charge-discharge at ambient temperature, first discharge specific capacity is 709mAh/g, after circulation 50 circle, specific discharge capacity is 685mAh/g, and efficiency is 99.3%.Different multiplying charge-discharge test is carried out under 80 DEG C of conditions, first circle 0.2C specific discharge capacity is 1355mAh/g, after circulation 5 circle, under 0.5C, specific discharge capacity is 790mAh/g, after circulation 10 circle, under 1C, specific discharge capacity is 699mAh/g, after circulation 15 circle, under 2C, specific discharge capacity is 598mAh/g, when multiplying power progressively gets back to 0.2C, after circulation 20 circle, specific discharge capacity is 812mAh/g, and efficiency is 98.9%.
Embodiment 5
Preparation component utilizes nano-sulfur, Graphene, the LiMn of Liquid preparation methods using sodium thiosulfate as sulphur source
2o
4composite positive pole, concrete preparation technology is as follows:
Prepare composite material: the sodium thiosulfate (Na taking 3.45g
2s
2o
3) and the polyvinylpyrrolidone (PVP) of 60mg be dissolved in the ultra-pure water of 100mL, by the Graphene of 0.1g and 0.15gLiMn
2o
4in the ultra-pure water of 50mL, by two kinds of solution mixing, 600r/min stirs 10h, then add the concentrated hydrochloric acid of 4.4mL10mol/L, at room temperature magnetic agitation 2 hours, filter, with a large amount of milli-Q water surplus materials, and under 50 DEG C of conditions vacuumize 24h, obtain black powder.By black powder heat treatment 20h under 155 DEG C of conditions in sealing tube furnace, and a straight-through argon gas is protected, and obtains nano-sulfur/Graphene/LiMn
2o
4in-situ composite.Prepared nano-sulfur/Graphene/LiMn
2o
4in composite material, the quality of sulphur accounts for 71% of gross mass.
Prepare anode pole piece: take nano-sulfur/Graphene/LiMn
2o
4composite material 0.14g, SuperP0.04g, polyacrylic acid (PAA) 0.02g, be placed in mortar grinding 30 minutes, then appropriate 1-METHYLPYRROLIDONE (NMP) is added, wet-milling 5 minutes, be coated in after being modulated into muddy and used on the aluminium foil of alcohol washes, dry in the baking oven of 50 DEG C, solvent flashing 12h, obtains the anode pole piece of lithium-sulfur cell.
Anode pole piece/lithium-sulfur cell ethers electrolyte/lithium sheet is utilized by the anode pole piece of prepared lithium-sulfur cell to be assembled into button cell, in room temperature, testing first circle specific discharge capacity under 0.2C is 1350mAh/g, and after circulation 100 circle, specific discharge capacity is 799mAh/g, and efficiency is 99.8%.Carry out the test of 0.1C rate charge-discharge at ambient temperature.First circle specific discharge capacity is 1480mAh/g, and after circulation 100 circle, specific discharge capacity is 986mAh/g, and efficiency is 99.8%.
Embodiment 6
Prepare and material proportion in embodiment 5, positive pole plate of lithium-sulfur cell that thickness is identical, be assembled into button cell, carry out the test of 1C rate charge-discharge at ambient temperature, first discharge specific capacity is 789mAh/g, after circulation 50 circle, specific discharge capacity is 705mAh/g, and efficiency is 99.5%.Different multiplying charge-discharge test is carried out under 80 DEG C of conditions, first circle 0.2C specific discharge capacity is 1384mAh/g, after circulation 5 circle, under 0.5C, specific discharge capacity is 823mAh/g, after circulation 10 circle, under 1C, specific discharge capacity is 719mAh/g, after circulation 15 circle, under 2C, specific discharge capacity is 648mAh/g, when multiplying power progressively gets back to 0.2C, after circulation 20 circle, specific discharge capacity is 848mAh/g, and efficiency is 99.6%.
Embodiment 7
Preparation component sublimed sulfur, carbon nano-fiber, LiNi
xco
ymn
zo
2composite positive pole, concrete preparation technology is as follows:
Prepare composite material: be first sublimed sulfur according to mass ratio: carbon nano-fiber: LiNi
xco
ymn
zo
2=6.5:2:1.5, adds the sublimed sulfur of 0.65g in the benzene of 40mL, the carbon nano-fiber of 0.2g and 0.15gLiNi respectively
xco
ymn
zo
2in the ultra-pure water of 60mL, benzene is mixed with ultra-pure water, the stirring 10h of 500r/min, at 60 DEG C, solvent evaporates is complete, with a large amount of milli-Q water surplus materials, and under 50 DEG C of conditions vacuumize 24h, obtain black powder.By black powder heat treatment 20h under 165 DEG C of conditions in sealing tube furnace, and a straight-through argon gas is protected, and is elevated sulphur/carbon nano-fiber/LiNi
xco
ymn
zo
2composite material.Prepared sublimed sulfur/carbon nano-fiber/LiNi
xco
ymn
zo
2in composite material, the quality of sulphur accounts for 59% of gross mass.
Prepare anode pole piece: take sublimed sulfur/carbon nano-fiber/LiNi
xco
ymn
zo
2composite material 0.14g, SuperP0.04g, polyacrylic acid (PAA) 0.02g, be placed in mortar grinding 30 minutes, then appropriate 1-METHYLPYRROLIDONE (NMP) is added, wet-milling 5 minutes, be coated in after being modulated into muddy and used on the aluminium foil of alcohol washes, dry in the baking oven of 50 DEG C, solvent flashing 12h, obtains the anode pole piece of lithium-sulfur cell.
Anode pole piece/lithium-sulfur cell ethers electrolyte/lithium sheet is utilized by the anode pole piece of prepared lithium-sulfur cell to be assembled into button cell, in room temperature, testing first circle specific discharge capacity under 0.2C is 1323mAh/g, and after circulation 100 circle, specific discharge capacity is 787mAh/g, and efficiency is 97.8%.Carry out the test of 0.1C rate charge-discharge at ambient temperature.First circle specific discharge capacity is 1380mAh/g, and after circulation 100 circle, specific discharge capacity is 974mAh/g, and efficiency is 99.2%.
Embodiment 8
Prepare and material proportion in embodiment 7, positive pole plate of lithium-sulfur cell that thickness is identical, be assembled into button cell, carry out the test of 1C rate charge-discharge at ambient temperature, first discharge specific capacity is 729mAh/g, after circulation 50 circle, specific discharge capacity is 679mAh/g, and efficiency is 99.3%.Different multiplying charge-discharge test is carried out under 80 DEG C of conditions, first circle 0.2C specific discharge capacity is 1224mAh/g, after circulation 5 circle, under 0.5C, specific discharge capacity is 801mAh/g, after circulation 10 circle, under 1C, specific discharge capacity is 679mAh/g, after circulation 15 circle, under 2C, specific discharge capacity is 568mAh/g, when multiplying power progressively gets back to 0.2C, after circulation 20 circle, specific discharge capacity is 832mAh/g, and efficiency is 99.6%.
Embodiment 9
Preparation component utilizes nano-sulfur, section's qin carbon black, the LiFePO of Liquid preparation methods using vulcanized sodium as sulphur source
4composite positive pole, concrete preparation technology is as follows:
Prepare composite material: the sodium sulfite of the vulcanized sodium and 6.3g that take 7.8g is dissolved in 50mL ultra-pure water, by 0.1g section qin carbon black and 0.2g lithium-containing transition metal oxide in the ultra-pure water of 50mL, by two kinds of solution mixing, stir 12h, then add the concentrated sulfuric acid that 8mL concentration is 98%, at room temperature magnetic agitation 1.5 hours, filter, with a large amount of milli-Q water surplus materials, and under 50 DEG C of conditions vacuumize 24h, obtain black powder.By black powder heat treatment 20h under 155 DEG C of conditions in sealing tube furnace, and a straight-through argon gas is protected, and obtains nano-sulfur/section qin carbon black/LiFePO
4in-situ composite.Prepared nano-sulfur/section qin carbon black/LiFePO
4in composite material, the quality of sulphur accounts for 65% of gross mass.
Prepare anode pole piece: take nano-sulfur/section qin carbon black/LiFePO
4composite material 0.14g, SuperP0.04g, polyacrylic acid (PAA) 0.02g, be placed in mortar grinding 30 minutes, then appropriate 1-METHYLPYRROLIDONE (NMP) is added, wet-milling 5 minutes, be coated in after being modulated into muddy and used on the aluminium foil of alcohol washes, dry in the baking oven of 50 DEG C, solvent flashing 12h, obtains the anode pole piece of lithium-sulfur cell.
Anode pole piece/lithium-sulfur cell ethers electrolyte/lithium sheet is utilized by the anode pole piece of prepared lithium-sulfur cell to be assembled into button cell, in room temperature, testing first circle specific discharge capacity under 0.2C is 1270mAh/g, and after circulation 100 circle, specific discharge capacity is 785mAh/g, and efficiency is 99.6%.Carry out the test of 0.1C rate charge-discharge at ambient temperature.First circle specific discharge capacity is 1443mAh/g, and after circulation 100 circle, specific discharge capacity is 954mAh/g, and efficiency is 99.5%.
Embodiment 10
Prepare and material proportion in embodiment 5, positive pole plate of lithium-sulfur cell that thickness is identical, be assembled into button cell, carry out the test of 1C rate charge-discharge at ambient temperature, first discharge specific capacity is 768mAh/g, after circulation 50 circle, specific discharge capacity is 685mAh/g, and efficiency is 99.2%.Different multiplying charge-discharge test is carried out under 80 DEG C of conditions, first circle 0.2C specific discharge capacity is 1374mAh/g, after circulation 5 circle, under 0.5C, specific discharge capacity is 805mAh/g, after circulation 10 circle, under 1C, specific discharge capacity is 714mAh/g, after circulation 15 circle, under 2C, specific discharge capacity is 652mAh/g, when multiplying power progressively gets back to 0.2C, after circulation 20 circle, specific discharge capacity is 831mAh/g, and efficiency is 99.2%.
Claims (14)
1. a lithium-sulfur battery composite anode material, is characterized in that: be composited by the raw material comprising elemental sulfur, conductive carbon material and lithium-containing transition metal oxide.
2. lithium-sulfur battery composite anode material according to claim 1, is characterized in that: be made up of following mass parts raw material components:
Elemental sulfur 50 ~ 80 parts;
Conductive carbon material 5 ~ 25 parts;
Lithium-containing transition metal oxide 5 ~ 25 parts.
3. lithium-sulfur battery composite anode material according to claim 2, is characterized in that: described conductive carbon material is at least one in section's qin carbon black, SuperP, acetylene black, Graphene, carbon nano-tube, carbon nano-fiber.
4. lithium-sulfur battery composite anode material according to claim 2, is characterized in that: described is Li containing lithium transiens metal oxide
4ti
5o
12, LiFePO
4, LiCoO
2, LiNiO
2, LiMnO
2, LiMn
2o
4, LiNi
xco
ymn
zo
2, nLi
2mO
3(1-n) LiMO
2in at least one, wherein M is Ni, Co, Fe or Ni
1/2mn
1/2.
5. lithium-sulfur battery composite anode material according to claim 2, is characterized in that: described elemental sulfur is nano elemental sulfur.
6. prepare the method for the lithium-sulfur battery composite anode material described in any one of Claims 1 to 5, it is characterized in that: comprise scheme a, scheme b or scheme c:
Scheme a: after the organic solution being dissolved with elemental sulfur and the aqueous solution being dispersed with conductive carbon material and lithium-containing transition metal oxide are uniformly mixed, solvent flashing, gained mixture is placed in heat treatment at 130 ~ 200 DEG C of temperature, to obtain final product;
Scheme b: after the solution containing sodium thiosulfate and polyvinylpyrrolidone is uniformly mixed with the aqueous solution being dispersed with conductive carbon material and lithium-containing transition metal oxide, continuing under the condition stirred, add hydrochloric acid reaction, after having reacted, solvent flashing, gained mixture is placed in heat treatment at 130 ~ 200 DEG C of temperature, to obtain final product;
Scheme c: after the solution of Containing Sulfur sodium and sodium sulfite and the aqueous solution being dispersed with conductive carbon material and lithium-containing transition metal oxide are uniformly mixed, continuing under the condition stirred, add sulfuric acid reaction, after having reacted, solvent flashing, gained mixture is placed in heat treatment at 130 ~ 200 DEG C of temperature, to obtain final product.
7. the method preparing lithium-sulfur battery composite anode material according to claim 6, is characterized in that:
In scheme b, the mass ratio of sodium thiosulfate and polyvinylpyrrolidone is 20 ~ 100:1; The mol ratio of sodium thiosulfate and hydrochloric acid is 1:2 ~ 3; Reaction time is 1 ~ 3h;
In scheme c, the mol ratio of vulcanized sodium, sodium sulfite and sulfuric acid is 2:1:3; Reaction time is 1 ~ 3h.
8. the method preparing lithium-sulfur battery composite anode material according to claim 6, is characterized in that: the time be uniformly mixed in scheme a, scheme b or scheme c is 10h ~ 30h.
9. the method preparing lithium-sulfur battery composite anode material according to claim 6, is characterized in that: in scheme a, scheme b or scheme c, solvent flashing realizes under 25 DEG C ~ 60 DEG C temperature conditions.
10. the method preparing lithium-sulfur battery composite anode material according to claim 6, is characterized in that: in scheme a, scheme b or scheme c, heat treatment time is 8h ~ 20h.
The application of the lithium-sulfur battery composite anode material described in 11. any one of Claims 1 to 5, is characterized in that: be applied to the positive pole preparing lithium-sulfur cell.
The application of 12. lithium-sulfur battery composite anode materials according to claim 11, it is characterized in that: after described lithium-sulfur battery composite anode material is mixed with conductive carbon material and binding agent tool, mill, add 1-METHYLPYRROLIDONE wet-milling again, be modulated into pureed slurry, be coated on aluminium foil, dry, obtain positive pole.
The application of 13. lithium-sulfur battery composite anode materials according to claim 12, is characterized in that: the mass ratio of lithium-sulfur battery composite anode material and conductive carbon material and binding agent is 65 ~ 75:15 ~ 25:10.
The application of 14. lithium-sulfur battery composite anode materials according to claim 13, is characterized in that: the mass ratio of lithium-sulfur battery composite anode material and SuperP conductive carbon material and polyacrylic acid binding agent is 70:20:10.
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