CN1803631A - Preparation method of multi-element nanometer sulfur anode material for lithium ion battery - Google Patents
Preparation method of multi-element nanometer sulfur anode material for lithium ion battery Download PDFInfo
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Abstract
The preparation method for nano composite anode material of V2O5-carbon-sulphur and LiVO3-carbon-sulphur comprises: using NH4VO3 or V2O5 as material to prepare V2O5 sol; grinding and mixing the carbon material (acetylene black, acetylene black or active carbon) and elemental sulfur; dispersing the said mixture into V2O5 sol; drying and thermal treating to obtain the nano V2O5-carbon-sulphur composite material; or dispersing the mixture into V2O5 sol contained LiOH to final obtain another LiVO3-carbon-sulphur composite material. Both the products have high electrochemical activity and high density. This invention has simple process and low cost.
Description
Technical field
The present invention relates to the preparation method of lithium ion battery with multi-element nanometer sulfur anode material, relate in particular to the preparation method of Vanadium Pentoxide in FLAKES-carbon-sulphur nano composite positive pole material and lithium vanadate-carbon-sulphur nano composite positive pole material, belong to chemical engineering and novel material preparation method technical field.
Background technology
Lithium ion battery is the novel high-energy secondary cell that twentieth century begins practicability the nineties, have that voltage height, energy density are big, outstanding advantages such as good cycle, self-discharge are little, memory-less effect, be widely used in field of portable devices such as mobile telephone, notebook computer, digital product, power tool.Lithium ion battery is as the applications well prospect that electrical source of power showed of electromobile and hybrid vehicle and in the huge applications potentiality of numerous areas such as military equipment, aerospace.
Since eighties of last century lithium ion battery at the beginning of the nineties comes out, with the graphitized carbon material is that negative pole, cobalt acid lithium material are that anodal lithium-ion electric pool technology has obtained huge development, is example with notebook computer with 18650 type batteries, about its specific energy was doubled in 10 years.At present, commercial lithium ion battery still mainly is that negative pole, cobalt acid lithium material are anodal with the graphitized carbon material.Along with developing rapidly of information technology, be the continuous miniaturization of handheld device, the intellectuality of representative with mobile telephone, notebook computer etc., require its power supply to have higher specific energy.In addition, field such as electromobile requires motive-power battery must have higher energy density, lower cost and better security.The performance of commodity lithium ion battery more and more can not satisfy the requirement of above-mentioned development, and wherein positive electrode material is one of important restraining factors.
The subject matter that lithium cobaltate cathode material exists is: (1) thermostability is lower, and the overcharging resisting ability is relatively poor, under high temperature or battery abuse condition, can cause catch fire, safety issue such as blast; (2) theoretical specific capacity is 274mAh/g, and is about actual specific capacity 140mAh/g, lower; (3) cost an arm and a leg, the cobalt metal valency was about about 400,000 yuan/ton in 2004.For overcoming these shortcomings, people are devoted to research and develop new positive electrode material always when cobalt acid lithium material is constantly carried out modification.Study more material and mainly contain following series: lithium nickelate series, as: LiNi
0.8Coi
0.2O
2Lithium manganate series comprises: lithium manganate having spinel structure is as LiMn
2-xCo
xO
4With layered lithium manganate as LiMn
0.5Ni
0.5O
2The nickle cobalt lithium manganate system, as: LiNi
1/3Co
1/3Mn
1/3O
2Iron lithium phosphate (LiFePO
4) etc.Though these material prices decrease than the sour lithium of cobalt, their specific storage and cobalt acid lithium difference are not very big, are difficult in to increase substantially on the lithium ion battery specific energy and accomplish something.
The theoretical specific capacity of sulphur is up to 1675mAhg-1, and as positive electrode material, basic metal is the secondary cell (as: sodium-sulfur cell that negative pole can be formed high-energy-density with sulphur, lithium-sulfur cell), in addition, sulphur also has advantages such as low price, reserves are abundant, nontoxicity, causes people's attention already.But because elemental sulfur exists electroconductibility low, its discharging product polysulfide easily dissolves in the electrolytic solution, causes problems such as the low and cycle performance difference of the utilization ratio of active substance, has restricted its commercialization process.What early succeed in developing is sodium-sulfur cell, is ionogen with the alumina-ceramic, about 300 ℃ of working temperatures, and sodium and sulphur all are in molten state to put forward doctor positive electroconductibility, and there is bigger potential safety hazard in this battery, is difficult to widespread use.In recent years, people begin to be devoted to the research of normal temperature lithium-sulfur cell.In order to overcome problems such as poorly conductive that elemental sulfur exists, discharging product dissolving, mainly take to prepare the method for sulphur matrix material.First kind is that sulphur and carbon are compound, carbon can improve the electroconductibility of sulfur electrode as conducting medium, also can play simultaneously the discharging product dissolved effect that suppresses sulphur to a certain extent, as: the gac of people such as the Zheng Wei of Harbin Institute of Technology preparation and the nano composite material of sulphur: power technology, 29 (8) 532).Second kind is that polymkeric substance and sulphur carry out chemical combination and prepares the organic polysulfide compound, as: people such as perichaud (U.S. Patent number US4,664,991) study polyacetylene, polystyrene, Polythiophene, polypyrrole, polyaniline and derivative thereof and sulfuration and closed the polysulfide of formation, people such as malkina (U.S. Patent number US6,117,590) many sulphur of synthetic polyacetylene multipolymer etc.These polysulfides have higher electroconductibility than elemental sulfur, but actual specific capacity reduces greatly, exist in the charge and discharge process because the small molecules that bond rupture forms is soluble in problems such as electrolytic solution.(CN02111404.8 such as Wang Jiulin; CN02111403.3; Adv Mater, 2002,14 (13-14): 963) utilize the polyacrylonitrile powder to mix with sublimed sulphur, thermal treatment has at a certain temperature prepared a kind of matrix material of partial vulcanization, specific storage and cycle performance all are better than above-mentioned polysulfide, but still not ideal enough aspect electroconductibility, density, processing characteristics etc.
The present invention prepares a kind of inorganic multivariate nanometer sulphur matrix material by nano elemental sulfur and nano-sized carbon are dispersed in the barium oxide colloid by certain thermal treatment.Wherein carbon material can make matrix material have good electron conduction; And barium oxide (V
2O
5, LiV
3O
8Or LiV
2O
5) itself also be anode active material of lithium ion battery, have preferably lithium ion conductive and have higher reversible lithium storage capacity; Simultaneously, carbon and barium oxide can play the fixedly diffusion and the dissolved effect of the discharging product of sulphur, prevention sulphur; In addition, this material is than sulfide polymer composite density height, and the processability of making electrode is good.
Summary of the invention
The objective of the invention is to propose the preparation method of a kind of lithium ion battery with Vanadium Pentoxide in FLAKES-carbon-sulphur nano composite positive pole material and lithium vanadate-carbon-sulphur nano composite positive pole material.Wherein lithium vanadate is LiV
3O
8Or LiV
2O
5With NH
4VO
3Or V
2O
5Chilling forms V after the high-temperature fusion in deionized water
2O
5Colloidal sol; Carbon material (acetylene black, carbon black or gac) is mixed with elemental sulfur material ball milling; Carbon, sulphur mixture thorough mixing are scattered in V
2O
5In the colloidal sol, drying, thermal treatment obtain V
2O
5-carbon-sulphur nano composite material.Carbon sulphur mixture thorough mixing is dispersed in the V that contains LiOH
2O
5In the colloidal sol, drying, thermal treatment obtain LiV
3O
8(or LiV
2O
5)-carbon-sulphur nano composite material.
The objective of the invention is to be achieved through the following technical solutions:
1. anode material for lithium-ion batteries V
2O
5The preparation method of-carbon-sulphur nano composite material, this method comprise following each step successively:
(1) takes by weighing a certain amount of ammonium meta-vanadate or V
2O
5, it is warming up to 800 ℃～900 ℃ fusions, in the deionized water with its chilling vigorous stirring under room temperature, make Vanadium Pentoxide in FLAKES colloidal sol then.
(2) take by weighing a certain amount of carbon material, carbon material can be a kind of in acetylene black, carbon black, the gac, takes by weighing a certain amount of elemental sulfur, and elemental sulfur can be sublimed sulphur or high purity sulphur.With ethanol is medium, under nitrogen or argon gas atmosphere, carbon and sulphur is carried out ball milling mix, and the mass ratio of carbon and sulphur is: 0.2: 1～1.2: 1.
(3) the Vanadium Pentoxide in FLAKES colloidal sol of carbon, sulphur mixture and step (1) preparation that ball milling in the step (2) is good places mechanical stirring mixing tank thorough mixing, and the mass ratio of sulphur and Vanadium Pentoxide in FLAKES is: 0.4: 1～2: 1.
(4) the resulting gluey slurry of step (3) is carried out spraying drying in spray-drying tower, input speed is that every liter of tower holds 20-60ml/h, produces atomizing under 0.1Mpa, and the control air inlet temperature is 250 ± 5 ℃, temperature out is 90 ± 5 ℃, makes spherical powder; Or place stoving oven to dry the resulting gluey slurry of step (3).
(5) with step (4) products therefrom under nitrogen or argon gas atmosphere in 200～300 ℃ of thermal treatments, obtain V
2O
5-carbon-sulphur nano composite material.
2. the preparation method of anode material for lithium-ion batteries lithium vanadate-carbon-sulphur nano composite material, this method comprises following each step successively:
(1) takes by weighing a certain amount of ammonium meta-vanadate or V
2O
5, it is warming up to 800 ℃～900 ℃ fusions, in the deionized water of chilling vigorous stirring under room temperature, make Vanadium Pentoxide in FLAKES colloidal sol then; By lithium, vanadium mol ratio is to take by weighing a certain amount of LiOHH in 1: 3 or 1: 2
2O is soluble in water, is added to then in the above-mentioned Vanadium Pentoxide in FLAKES colloidal sol, stirs 15 minutes.
(2) take by weighing a certain amount of carbon material, carbon material can be a kind of in acetylene black, carbon black, the gac, takes by weighing a certain amount of elemental sulfur, and elemental sulfur can be sublimed sulphur or high purity sulphur.With ethanol is medium, under nitrogen or argon gas atmosphere, carbon and sulphur is carried out ball milling mix, and the mass ratio of carbon and sulphur is: 0.2: 1～1.2: 1.
(3) the Vanadium Pentoxide in FLAKES colloidal sol that contains LiOH of carbon, sulphur mixture and step (1) preparation that ball milling in the step (2) is good places mechanical stirring mixing tank thorough mixing, and the mass ratio of sulphur and Vanadium Pentoxide in FLAKES is: 0.4: 1～2: 1.
(4) the resulting gluey slurry of step (3) is carried out spraying drying in spray-drying tower, input speed is that every liter of tower holds 20-60ml/h, produces atomizing under 0.1Mpa, and the control air inlet temperature is 250 ± 5 ℃, temperature out is 90 ± 5 ℃, makes spherical powder; Or place stoving oven to dry the resulting gluey slurry of step (3).
(5) with step (4) products therefrom under nitrogen or argon gas atmosphere in 200～300 ℃ of thermal treatments, obtain LiV
3O
8(or LiV
2O
5)-carbon-sulphur nano composite material.
The method for preparing polynary nanometer sulphur matrix material provided by the invention has the following advantages: the matrix material electrochemical activity height of preparation, can be made into spheroidal particle, the density height, the cost of material is low, technical process is simple, has very big using value.
Embodiment
The invention provides a kind of preparation anode material for lithium-ion batteries V
2O
5-carbon-sulphur nano composite material and a kind of method for preparing lithium vanadate-carbon-sulphur nano composite material, its concrete implementation step is as follows:
1. anode material for lithium-ion batteries V
2O
5The preparation method of-carbon-sulphur nano composite material, this method comprise following each step successively:
(1) takes by weighing a certain amount of ammonium meta-vanadate or V
2O
5, it is warming up to 800 ℃～900 ℃ fusions, in the deionized water with its chilling vigorous stirring under room temperature, make Vanadium Pentoxide in FLAKES colloidal sol then.
(2) take by weighing a certain amount of carbon material, carbon material can be a kind of in acetylene black, carbon black, the gac, takes by weighing a certain amount of elemental sulfur, and elemental sulfur can be sublimed sulphur or high purity sulphur.With ethanol is medium, under nitrogen or argon gas atmosphere, carbon and sulphur is carried out ball milling mix, and the mass ratio of carbon and sulphur is: 0.2: 1～1.2: 1.
(3) the Vanadium Pentoxide in FLAKES colloidal sol of carbon, sulphur mixture and step (1) preparation that ball milling in the step (2) is good places mechanical stirring mixing tank thorough mixing, and the mass ratio of sulphur and Vanadium Pentoxide in FLAKES is: 0.4: 1～2: 1.
(4) the resulting gluey slurry of step (3) is carried out spraying drying in spray-drying tower, input speed is that every liter of tower holds 20-60ml/h, produces atomizing under 0.1Mpa, and the control air inlet temperature is 250 ± 5 ℃, temperature out is 90 ± 5 ℃, makes spherical powder; Or place stoving oven to dry the resulting gluey slurry of step (3).
(5) with step (4) products therefrom under nitrogen or argon gas atmosphere in 200～300 ℃ of thermal treatments, obtain V
2O
5-carbon-sulphur nano composite material.
2. the preparation method of anode material for lithium-ion batteries lithium vanadate-carbon-sulphur nano composite material, this method comprises following each step successively:
(1) takes by weighing a certain amount of ammonium meta-vanadate or V
2O
5, it is warming up to 800 ℃～900 ℃ fusions, in the deionized water of chilling vigorous stirring under room temperature, make Vanadium Pentoxide in FLAKES colloidal sol then; By lithium, vanadium mol ratio is to take by weighing a certain amount of LiOHH in 1: 3 or 1: 2
2O is soluble in water, is added to then in the above-mentioned Vanadium Pentoxide in FLAKES colloidal sol, stirs 15 minutes.
(2) take by weighing a certain amount of carbon material, carbon material can be a kind of in acetylene black, carbon black, the gac, takes by weighing a certain amount of elemental sulfur, and elemental sulfur can be sublimed sulphur or high purity sulphur.With ethanol is medium, under nitrogen or argon gas atmosphere, carbon and sulphur is carried out ball milling mix, and the mass ratio of carbon and sulphur is: 0.2: 1～1.2: 1.
(3) the Vanadium Pentoxide in FLAKES colloidal sol that contains LiOH of carbon, sulphur mixture and step (1) preparation that ball milling in the step (2) is good places mechanical stirring mixing tank thorough mixing, and the mass ratio of sulphur and Vanadium Pentoxide in FLAKES is: 0.4: 1～2: 1.
(4) the resulting gluey slurry of step (3) is carried out spraying drying in spray-drying tower, input speed is that every liter of tower holds 20-60ml/h, produces atomizing under 0.1Mpa, and the control air inlet temperature is 250 ± 5 ℃, temperature out is 90 ± 5 ℃, makes spherical powder; Or place stoving oven to dry the resulting gluey slurry of step (3).
(5) with step (4) products therefrom under nitrogen or argon gas atmosphere in 200～300 ℃ of thermal treatments, obtain LiV
3O
8(or LiV
2O
5)-carbon-sulphur nano composite material.
Introduce embodiments of the invention below:
Embodiment one: take by weighing 30gNH
4VO
3Insert in the corundum crucible, in retort furnace, it was warming up to 850 ℃ of fusions in 3 hours, be incubated after 1 hour, make V in the deionized water of chilling vigorous stirring under room temperature
2O
5Colloidal sol; Take by weighing 10g carbon black, 20g sublimed sulphur, 20ml dehydrated alcohol and place the stainless steel vessel of ball mill, abrading-ball is a Stainless Steel Ball, nitrogen protection, and the rotating speed of ball milling is 500 rev/mins, 20 hours ball milling time; With material behind the ball milling and prepared V
2O
5Colloidal sol places the mechanical agitation type mixing tank, and the volume of mixing tank is 1 liter, 2000 rev/mins of stirring velocitys, churning time 1 hour; Material through mixing is transferred in the disk, places retort furnace, 80 ℃ of oven dry under air atmosphere; Material after the oven dry is placed the atmosphere protection stove, and 250 ℃ of constant temperature were heat-treated in 3 hours in nitrogen atmosphere, were cooled to room temperature naturally; Take out material and pulverize in grinding alms bowl, 300 orders sieve, and get product V
2O
5-carbon-sulphur nano composite material.
Take by weighing this sample 20mg,, be applied on the aluminium foil substrate sample powder, acetylene black and PTFE mixed with 8: 1: 1, be pressed into electrode slice, after vacuum-drying,, make negative pole with the pure metal lithium sheet as anodal, Celgard2400 is a barrier film, EC+DEC (1: 1)+1M LiPF
6Be electrolytic solution, make button cell.Recording this sample is 0.5mA/cm in current density
2The time the round-robin specific discharge capacity second time be 607mAh/g, the 20th time the round-robin loading capacity is 594mAh/g.
Embodiment two: take by weighing 50gNH
4VO
3Insert in the corundum crucible, in retort furnace, it was warming up to 900 ℃ of fusions in 3 hours, be incubated after 1 hour, make V in the deionized water of chilling vigorous stirring under room temperature
2O
5Colloidal sol; Take by weighing 4g carbon black, 20g high purity sulphur and 20ml dehydrated alcohol and carry out ball milling; Heat-treat condition was changed into 200 ℃ of constant temperature 3 hours by 250 ℃ of constant temperature of embodiment one in 3 hours; Other condition is identical with embodiment one, makes V
2O
5-carbon black-sulphur nano composite material.The round-robin specific discharge capacity second time that records this sample with the testing method identical with embodiment one is 550mAh/g, and the 20th time the round-robin loading capacity is 543mAh/g.
Embodiment three: NH
4VO
3Amount change 16.5g into by the 30g of embodiment one, the amount of carbon black changes 24g into by the 10g of embodiment one, other condition is identical with embodiment one, makes V
2O
5-carbon black-sulphur nano composite material.The round-robin specific discharge capacity second time that records this sample with the testing method identical with embodiment one is 552mAh/g, and the 20th time the round-robin loading capacity is 548mAh/g.
Embodiment four: take by weighing 18.3g V
2O
530gNH in the alternate embodiment one
4VO
3, insert in the corundum crucible, in retort furnace, it was warming up to 800 ℃ of fusions in 3 hours, be incubated after 1 hour, make V in the deionized water of chilling vigorous stirring under room temperature
2O
5Colloidal sol; Heat-treat condition changed in argon gas gas atmosphere 300 ℃ of constant temperature 3 hours in 3 hours into by 250 ℃ of constant temperature in nitrogen atmosphere of embodiment one; Other condition is identical with embodiment one, is prepared into V
2O
5-carbon black-sulphur nano composite material.The round-robin specific discharge capacity second time that the testing method identical with embodiment one records this sample is 615mAh/g, and the 20th time the round-robin loading capacity is 603mAh/g.
Embodiment five: change the carbon black among the embodiment one into acetylene black, other condition is identical with embodiment one, makes V
2O
5-acetylene black-sulphur nano composite material.The round-robin specific discharge capacity second time that records this sample with the testing method identical with embodiment one is 616mAh/g.The 20th time the round-robin loading capacity is 607mAh/g.
Embodiment six: change the carbon black among the embodiment one into gac, other condition is identical with embodiment one, makes V
2O
5-gac-sulphur nano composite material.The round-robin specific discharge capacity second time that records this sample with the testing method identical with embodiment one is 605mAh/g.The 20th time the round-robin loading capacity is 598mAh/g.
Embodiment seven: use the spray-drying tower spraying drying, the V of carbon black, sulphur with changing into retort furnace exsiccant step among the embodiment one
2O
5The input speed of colloidal sol is 20 ml/min, and spray pressure 0.1Mpa, temperature of inlet air are 250 ℃, and temperature out is 90 ℃; Other step is identical with embodiment one with condition.Make spherical V
2O
5-carbon black-sulphur nano composite material.The round-robin specific discharge capacity second time that the testing method identical with embodiment one records this sample is 611mAh/g, and the 20th time the round-robin loading capacity is 602mAh/g.。
Embodiment eight: take by weighing 30gNH
4VO
3Insert in the corundum crucible, in retort furnace, it was warming up to 800 ℃ of fusions in 3 hours, be incubated after 1 hour, make V in the deionized water of chilling vigorous stirring under room temperature
2O
5Colloidal sol; At V
2O
5(amount of the LiOH that is added is Li in molar ratio: V=1: 3 proportional arrangement), stirred 15 minutes, obtain containing the V of LiOH to add LiOH solution in the colloidal sol
2O
5V in the colloidal sol alternate embodiment one
2O
5Colloidal sol; Other condition is with embodiment one.Make LiV
3O
8-carbon black-sulphur nano composite material.The round-robin specific discharge capacity second time that the testing method identical with embodiment one records this sample is 587mAh/g, and the 20th time the round-robin loading capacity is 580mAh/g.
Embodiment nine: use the spray-drying tower spraying drying, the V of carbon black, sulphur, LiOH with changing into retort furnace exsiccant step among the embodiment eight
2O
5The input speed of colloidal sol is 20 ml/min, and spray pressure 0.1Mpa, temperature of inlet air are 250 ℃, and temperature out is 90 ℃.Other condition is identical with embodiment eight.Make spherical LiV
3O
8-carbon black-sulphur nano composite material.The round-robin specific discharge capacity second time that records this sample with the testing method identical with embodiment one is 592mAh/g, and the 20th time the round-robin loading capacity is 586mAh/g.
Embodiment ten: at V
2O
5The content of LiOH is that Li, V mol ratio are 1: 2 in the colloidal sol, and other condition is identical with embodiment eight.Make LiV
2O
5-carbon black-sulphur composite nano-powder material.With the testing method identical with embodiment one record this sample for the second time the round-robin specific discharge capacity be 585mAh/g, the 20th time the round-robin loading capacity is 580mAh/g.
Comparing embodiment one: take by weighing the stainless steel vessel that 20g carbon black, 20g sublimed sulphur, 20ml dehydrated alcohol place ball mill, abrading-ball is a Stainless Steel Ball, nitrogen protection, and the rotating speed of ball milling is 500 rev/mins, 20 hours ball milling time; Material behind the ball milling is transferred in the disk, places retort furnace, 80 ℃ of oven dry under air atmosphere; Material after the oven dry is placed the atmosphere protection stove, and 250 ℃ of constant temperature were heat-treated in 3 hours in nitrogen atmosphere, were cooled to room temperature naturally; Obtain two yuan of nano composite materials of carbon-sulphur.With the testing method identical with embodiment one record this sample for the second time the round-robin specific discharge capacity be 626mAh/g, the 20th time the round-robin loading capacity is 378mAh/g.
Comparing embodiment two: with NH
4VO
3Amount change 5g into by 30g, other step is identical with embodiment one with condition, makes matrix material.With the testing method identical with embodiment one record this sample for the second time the round-robin specific discharge capacity be 630mAh/g, the 20th time the round-robin loading capacity is 422mAh/g.
Comparing embodiment three: press the conditional operation of embodiment two, wherein NH
4VO
3Amount change 80g into by 30g, other condition is identical with embodiment one, the matrix material that makes round-robin specific discharge capacity for the second time is 412mAh/g, the 20th time the round-robin loading capacity is 405mAh/g.
Comparing embodiment four: press the conditional operation of embodiment one, it is identical with embodiment one wherein not add other condition of carbon black, and the round-robin specific discharge capacity second time that makes matrix material is 346mAh/g, and the 20th time the round-robin loading capacity is 219mAh/g.
Comparing embodiment five: press the conditional operation of embodiment four, wherein the amount of carbon black is changed into 2g by 10g, other condition is identical with embodiment four.The round-robin specific discharge capacity second time that makes matrix material is 422mAh/g, and the 20th time the round-robin loading capacity is 357mAh/g.
Claims (6)
1, a kind of anode material for lithium-ion batteries V
2O
5The preparation method of-carbon-sulphur nano composite material is characterized in that, this preparation method may further comprise the steps:
(1) takes by weighing-quantitative ammonium meta-vanadate or V
2O
5, it is warming up to 800 ℃～900 ℃ fusions, in the deionized water with its chilling vigorous stirring under room temperature, make Vanadium Pentoxide in FLAKES colloidal sol then;
(2) taking by weighing a certain amount of carbon material and a certain amount of elemental sulfur, is medium with ethanol, under nitrogen or argon gas atmosphere, carbon and sulphur is carried out ball milling mix, and the mass ratio of carbon and sulphur is: 0.2: 1～1.2: 1;
(3) the Vanadium Pentoxide in FLAKES colloidal sol of carbon, sulphur mixture and step (1) preparation that ball milling in the step (2) is good places mechanical stirring mixing tank thorough mixing, and the mass ratio of sulphur and Vanadium Pentoxide in FLAKES is: 0.4: 1～2: 1;
(4) the resulting gluey slurry of step (3) is carried out spraying drying in spray-drying tower, make spherical powder;
(5) with step (4) products therefrom under nitrogen or argon gas atmosphere in 200～300 ℃ of thermal treatments, obtain V
2O
5-carbon-sulphur nano composite material.
2, the preparation method of a kind of anode material for lithium-ion batteries lithium vanadate-carbon-sulphur nano composite material is characterized in that, this preparation method may further comprise the steps:
(1) takes by weighing a certain amount of ammonium meta-vanadate or V
2O
5, it is warming up to 800 ℃～900 ℃ fusions, in the deionized water of chilling vigorous stirring under room temperature, make Vanadium Pentoxide in FLAKES colloidal sol then; By lithium, vanadium mol ratio is to take by weighing a certain amount of LiOHH in 1: 3 or 1: 2
2O is soluble in water, is added to then in the above-mentioned Vanadium Pentoxide in FLAKES colloidal sol, stirs 15 minutes;
(2) taking by weighing a certain amount of carbon material and a certain amount of elemental sulfur, is medium with ethanol, under nitrogen or argon gas atmosphere, carbon and sulphur is carried out ball milling mix, and the mass ratio of carbon and sulphur is; 0.2: 1～1.2: 1;
(3) the Vanadium Pentoxide in FLAKES colloidal sol that contains LiOH of carbon, sulphur mixture and step (1) preparation that ball milling in the step (2) is good places mechanical stirring mixing tank thorough mixing, and the mass ratio of sulphur and Vanadium Pentoxide in FLAKES is: 0.4: 1～2: 1;
(4) the resulting gluey slurry of step (3) is carried out spraying drying in spray-drying tower, make spherical powder;
(5) with step (4) products therefrom under nitrogen or argon gas atmosphere in 200～300 ℃ of thermal treatments, obtain LiV
3O
8-carbon-sulphur nano composite material or LiV
2O
5-carbon-sulphur nano composite material.
3, a kind of anode material for lithium-ion batteries V according to claim 1
2O
5The preparation method of the described a kind of anode material for lithium-ion batteries lithium vanadate-carbon of the preparation method of-carbon-sulphur nano composite material or claim 2-sulphur nano composite material, it is characterized in that step (4) makes spherical powder for the resulting gluey slurry of step (3) being placed the stoving oven oven dry.
4, a kind of anode material for lithium-ion batteries V according to claim 1
2O
5The preparation method of the described a kind of anode material for lithium-ion batteries lithium vanadate-carbon of the preparation method of-carbon-sulphur nano composite material or claim 2-sulphur nano composite material is characterized in that described carbon material is acetylene black, carbon black or gac.
5, a kind of anode material for lithium-ion batteries V according to claim 1
2O
5The preparation method of the described a kind of anode material for lithium-ion batteries lithium vanadate-carbon of the preparation method of-carbon-sulphur nano composite material or claim 2-sulphur nano composite material is characterized in that described elemental sulfur is sublimed sulphur or high purity sulphur.
6, a kind of anode material for lithium-ion batteries V according to claim 1
2O
5The preparation method of the described a kind of anode material for lithium-ion batteries lithium vanadate-carbon of the preparation method of-carbon-sulphur nano composite material or claim 2-sulphur nano composite material, it is characterized in that, described spraying drying input speed is that every liter of tower holds 20-60ml/h, under 0.1Mpa, produce atomizing, the control air inlet temperature is 250 ± 5 ℃, and temperature out is 90 ± 5 ℃.
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Cited By (8)
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| CN101841036A (en) * | 2010-05-26 | 2010-09-22 | 耿世达 | Multi-sulfur carbon nanofiber composite cathode material for lithium ion battery and manufacturing method |
| WO2011023110A1 (en) * | 2009-08-25 | 2011-03-03 | Positec Group Limited | Lithium sulphur battery |
| CN102364728A (en) * | 2011-11-02 | 2012-02-29 | 上海交通大学 | Positive electrode material for lithium ion cells and preparation method thereof |
| CN103151554A (en) * | 2009-08-25 | 2013-06-12 | 苏州宝时得电动工具有限公司 | Lithium sulphur battery |
| CN106328946A (en) * | 2016-09-05 | 2017-01-11 | 长春劲能科技集团股份有限公司 | Method for preparing nano-micro carbon-sulfur composite by in-situ carbon coating of sulfur |
| CN106784738A (en) * | 2017-02-13 | 2017-05-31 | 湘潭大学 | A kind of mg-doped vanadic anhydride/carbon composite anode material and preparation method thereof |
| CN108963206A (en) * | 2018-06-14 | 2018-12-07 | 渤海大学 | A kind of V for potassium sulphur cell positive electrode2O5The preparation method of/S/PVA composite material and its electrode slice |
| CN109244394A (en) * | 2018-08-28 | 2019-01-18 | 上海交通大学 | Hollow vanadium dioxide/sulfur compound of lithium sulfur battery anode material and preparation method thereof |
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- 2005-12-23 CN CNA2005101307126A patent/CN1803631A/en active Pending
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| CN103151554A (en) * | 2009-08-25 | 2013-06-12 | 苏州宝时得电动工具有限公司 | Lithium sulphur battery |
| WO2011023110A1 (en) * | 2009-08-25 | 2011-03-03 | Positec Group Limited | Lithium sulphur battery |
| CN103151554B (en) * | 2009-08-25 | 2016-08-03 | 苏州宝时得电动工具有限公司 | Lithium-sulfur cell |
| CN101997145B (en) * | 2009-08-25 | 2013-06-05 | 苏州宝时得电动工具有限公司 | Lithium sulfur battery |
| CN101841036A (en) * | 2010-05-26 | 2010-09-22 | 耿世达 | Multi-sulfur carbon nanofiber composite cathode material for lithium ion battery and manufacturing method |
| CN102364728B (en) * | 2011-11-02 | 2013-05-29 | 上海交通大学 | Positive electrode material for lithium ion cells and preparation method thereof |
| CN102364728A (en) * | 2011-11-02 | 2012-02-29 | 上海交通大学 | Positive electrode material for lithium ion cells and preparation method thereof |
| CN106328946A (en) * | 2016-09-05 | 2017-01-11 | 长春劲能科技集团股份有限公司 | Method for preparing nano-micro carbon-sulfur composite by in-situ carbon coating of sulfur |
| CN106328946B (en) * | 2016-09-05 | 2019-04-12 | 长春劲能科技集团股份有限公司 | A kind of method that original position carbon coating sulphur prepares nano-micro structure carbon sulphur composite material |
| CN106784738A (en) * | 2017-02-13 | 2017-05-31 | 湘潭大学 | A kind of mg-doped vanadic anhydride/carbon composite anode material and preparation method thereof |
| CN108963206A (en) * | 2018-06-14 | 2018-12-07 | 渤海大学 | A kind of V for potassium sulphur cell positive electrode2O5The preparation method of/S/PVA composite material and its electrode slice |
| CN108963206B (en) * | 2018-06-14 | 2021-03-19 | 渤海大学 | V for positive electrode of potassium-sulfur battery2O5Preparation method of/S/PVA composite material and electrode plate thereof |
| CN109244394A (en) * | 2018-08-28 | 2019-01-18 | 上海交通大学 | Hollow vanadium dioxide/sulfur compound of lithium sulfur battery anode material and preparation method thereof |
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