CN109768265A - A kind of lithium ion battery negative material and preparation method thereof - Google Patents
A kind of lithium ion battery negative material and preparation method thereof Download PDFInfo
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- CN109768265A CN109768265A CN201910172794.2A CN201910172794A CN109768265A CN 109768265 A CN109768265 A CN 109768265A CN 201910172794 A CN201910172794 A CN 201910172794A CN 109768265 A CN109768265 A CN 109768265A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention relates to lithium ion battery negative materials of a kind of height ratio capacity and preparation method thereof, the material is a kind of zinc sulphide based on zinc sulphide hollow Nano spherical structure-zinc selenide composite material, preparation method is first to prepare zinc sulphide hollow nano-sphere, adds selenium powder by grinding and heats zinc sulphide hollow Nano ball surface selenizing.Present invention introduces zinc sulphide as negative electrode material, zinc sulphide-zinc selenide composite material is obtained using simple selenylation reaction, the material has significant structural advantage, it is possible to provide more oxidation activity sites have good mechanical performance and cycle life to obtain higher specific capacity.As negative electrode material active material, the two, which acts synergistically, can promote the chemical property of lithium ion battery for zinc sulphide and zinc selenide.
Description
Technical field
Technical solution of the present invention is related to a kind of lithium ion battery negative material and preparation method thereof of height ratio capacity, especially
It is related to a kind of zinc sulphide-zinc selenide composite lithium ion battery cathode material and preparation method thereof, belongs to technical field of material chemistry.
Background technique
Although economy and science and technology are fast-developing since 21 century, the main source of the energy is still with limited stone
Based on the fossil fuels such as oil, coal and natural gas.It is well known that the gaseous contamination discharged from fossil fuel and biomass fuel
Atmosphere brings serious environmental problem.Therefore, in face of increasingly serious energy and environmental problem, reproducible cleaning energy is developed
Source is own through becoming a problem in the urgent need to address.New energy refers to the unconventional energy developed and used on the basis of new technology
Source, including wind energy, solar radiant energy, ocean energy, geothermal energy, biomass energy, ammonia energy and nuclear energy etc..New forms of energy resource potentiality are big,
Meet energy demand, improve energy resource structure, reduce environmental pollution, in terms of oneself has played important function.
However, the electric power that the new energies such as wind energy, solar energy issue has unstability and discontinuity, it is difficult to directly apply to production
Life.Therefore, efficient energy storage and energy conversion device is established unstable power collection is got up and in due course will
Its steady release has great importance.
Compared with other rechargeable batteries (such as lead-acid battery, nickel-metal hydride battery), lithium ion battery has specific capacity height, circulation
Service life length, voltage platform height, memory-less effect, fast charging and discharging, security performance are high, self-discharge rate is low, environmental pollution is small, body
The apparent advantages such as long-pending small and light weight, therefore, lithium ion battery has been widely used for mobile phone, camera, laptop
Equal small size digitals equipment, and just sent out towards the energy-storage battery direction of the electric vehicle battery and wind energy of enlargement and solar energy
Exhibition.More stringent requirements are proposed for this performance to lithium ion battery, and the important component as lithium ion battery, positive and negative anodes
Material is the key factor for determining its performance.Therefore, it is aobvious that high-performance, the lithium ion battery electrode material of low cost are researched and developed
It must become more and more important.
Summary of the invention
The present invention is mentioned for the problems such as reversible capacity is smaller, cycle performance is poor present in current graphite cathode material
For a kind of lithium ion battery negative material and preparation method thereof.
The technical scheme adopted by the invention is that:
A kind of lithium ion battery negative material, the negative electrode material add selenium powder, borrow by first preparing zinc sulphide hollow nano-sphere
It is negative that zinc sulphide-zinc selenide composite lithium ion cell is prepared in zinc sulphide hollow Nano ball surface selenizing by assistant research fellow's mill and heating
Pole material.
A kind of lithium ion battery negative material preparation method, comprising the following steps:
(1) zinc sulphide hollow nano-sphere is prepared:
It measures zinc chloride and thiocarbamide is dissolved in obtained solution A in a certain amount of distilled water, solution A mass fraction is 1%~10%, another to claim
Appropriate amounts of gelatin is taken to be added in a certain amount of distilled water, the heating stirring in water-bath, until Gelatin obtained solution B, B solution matter
Measuring score is 1%~10%.It is stirred 10~30 minutes after two kinds of solution of A, B are mixed, is transferred to the high pressure of polytetrafluoroethyllining lining
Reaction kettle high temperature is calcined, and after cooled to room temperature, by the way that product is collected by centrifugation, is then washed with distilled water and dehydrated alcohol
Three times, it is dried in 60 DEG C of baking ovens, zinc sulfide nano-sphere is made.
(2) zinc selenide-zinc sulphide composite material is prepared:
It takes the zinc sulphide hollow nano-sphere prepared in step (1) to mix with selenium powder and grinds uniformly, be placed in tube furnace, in argon gas
High-temperature calcination under atmosphere can be prepared by zinc selenide-zinc sulphide composite material after cooling.
Further, the quality of zinc chloride needed for preparing solution A in the step (1) is 0.5~1g, and thiocarbamide quality is 1
~2g, distilled water volume are 50~100mL；
Further, gelatin quality needed for preparing solution B in the step (1) is 0.5~1g, distilled water volume is 50~
100mL；The condition of heating and stirring is 60~80 DEG C；
Step (1) the high temperature calcination condition is to be heated to 100~150 DEG C, and kept for 12~24 hours；
Further, zinc sulphide hollow nano-sphere and selenium powder mass ratio are 20~10:1 in the step (2)；
Step (2) the high temperature calcination condition is 400~600 DEG C, keeps the temperature 3~6h；
Advantageous effects of the invention are as follows:
The present invention introduces zinc sulphide when preparing lithium ion battery negative material as negative electrode material, and Zr-based materials are all the time all
Show preferable cycle performance, in addition China's zinc reserves abundant, so that this material becomes pole and has industrial application prospect
One of negative electrode material.At the same time, to sulfide research shows that the presence of element sulphur can be with buffer metal and lithium in alloy
Bulk effect during change further strengthens the stability of structure.
The present invention obtains zinc sulphide hollow nano-sphere during introducing zinc sulphide, by introducing gelatin as auxiliary,
Hollow ball structure possesses significant structural advantage when as lithium ion battery negative material, and uniform duct ensures on shell
Electrolyte enters inside more shells in which can be convenient, so that electrolyte is adequately contacted with active material, provides more oxidations
Active site obtains higher specific capacity at higher current densities.Zinc sulphide hollow sphere is made of zinc sulfide nano crystal, is shortened
The transmission path of electronics and charge, and internal free volume can alleviate the expansion of in charge and discharge process material, in addition
The good mechanical performance of material, so that hollow structure material possesses good cycle life.
The present invention utilizes simple selenylation reaction on the basis of introducing zinc sulphide, is not destroying zinc sulphide hollow ball structure
On the basis of by its surface progress selenizing obtain zinc sulphide-zinc selenide composite material, metal selenide is as metal chalcogenide chemical combination
One kind of object, since selenium atom is bigger than sulphur atom diameter, metallicity is stronger, so that metal selenide has compared with metal sulfide
Higher conductivity, this makes metal selenide have more advantage than metal sulfide in electrochemical energy storage and electro-catalysis field.This hair
Bright while introducing zinc sulphide and zinc selenide as negative electrode material active material, the two acts synergistically, and promotes lithium ion battery jointly
Chemical property.
Detailed description of the invention
Fig. 1 is zinc selenide-electric discharge of the zinc sulphide composite material as lithium ion battery negative material obtained by embodiment 1
Specific capacity circulation figure.
Fig. 2 is zinc selenide-multiplying power of the zinc sulphide composite material as lithium ion battery negative material obtained by embodiment 1
Performance map.
Specific embodiment
Embodiment 1:
(1) zinc sulphide hollow nano-sphere is prepared:
0.8g zinc chloride and 1.5g thiocarbamide are dissolved in 80mL distilled water (solution A), separately weigh 0.8g gelatin and 80mL distillation is added
In water, the heating stirring in water-bath, until Gelatin (solution B).It stirs 20 minutes, is transferred to after two kinds of solution are mixed
In the autoclave of polytetrafluoroethyllining lining.Reaction kettle is heated to 100~150 DEG C, and is kept for 12 hours.It naturally cools to
After room temperature, by the way that product is collected by centrifugation, is washed three times with distilled water and dehydrated alcohol, dried in 60 DEG C of baking ovens.
(2) zinc selenide-zinc sulphide composite material is prepared:
It takes the zinc sulphide hollow nano-sphere prepared in step (1) to mix with selenium powder according to mass ratio 15:1 and grinds uniformly, be placed in
In tube furnace, it is warming up to 500 DEG C under an argon atmosphere, keeps the temperature 4h, then cools to room temperature with the furnace.
Fig. 1 is the specific discharge capacity circulation figure using the test of new prestige charge-discharge test instrument, it may be seen that in 200mA/g
Under current density, the discharge capacity for the first time of the material is up to 796mAh/g, and the circulation by 50 circles still has 691mAh/g, instead
The negative electrode material should be gone out with good electrochemistry cycle performance.
Fig. 2 is the high rate performance figure of lithium ion battery negative material obtained by embodiment 1.As seen from the figure, though
Under the high current density of 2000mA/g, preparation-obtained lithium ion battery still shows the capacity of 338mAh/g, and when electricity
When current density is down to 200mA/g again, specific discharge capacity restores again to 611mAh/g, and it is excellent that this shows that the negative electrode material has
High rate performance.
Embodiment 2:
(1) zinc sulphide hollow nano-sphere is prepared:
0.5g zinc chloride and 1g thiocarbamide are dissolved in 50mL distilled water (solution A), separately weigh 0.5g gelatin and 50mL distilled water is added
In, 60 DEG C of heating stirrings in water-bath, until Gelatin (solution B).It stirs 10 minutes, shifts after two kinds of solution are mixed
Into the autoclave of polytetrafluoroethyllining lining.Reaction kettle is heated to 100 DEG C, and is kept for 12 hours.Naturally cool to room
Then Wen Hou is washed three times with distilled water and dehydrated alcohol, is dried in 60 DEG C of baking ovens by the way that product is collected by centrifugation.
(2) zinc selenide-zinc sulphide composite material is prepared:
It takes the zinc sulphide hollow nano-sphere prepared in step (1) to mix with selenium powder according to mass ratio 20:1 and grinds uniformly, be placed in
In tube furnace, it is warming up to 400 DEG C under an argon atmosphere, keeps the temperature 3h, then cools to room temperature with the furnace.
Embodiment 3:
(1) zinc sulphide hollow nano-sphere is prepared:
1g zinc chloride and 2g thiocarbamide are dissolved in 100mL distilled water (solution A), separately weigh 1g gelatin and are added in 100mL distilled water,
80 DEG C of heating stirrings in water-bath, until Gelatin (solution B).It stirs 30 minutes, is transferred to after two kinds of solution are mixed
In the autoclave of polytetrafluoroethyllining lining.Reaction kettle is heated to 150 DEG C, and is kept for 24 hours.Cooled to room temperature
Afterwards, it by the way that product is collected by centrifugation, is then washed three times with distilled water and dehydrated alcohol, is dried in 60 DEG C of baking ovens.
(2) zinc selenide-zinc sulphide composite material is prepared:
It takes the zinc sulphide hollow nano-sphere prepared in step (1) to mix with selenium powder according to mass ratio 10:1 and grinds uniformly, be placed in
In tube furnace, it is warming up to 600 DEG C under an argon atmosphere, keeps the temperature 6h, then cools to room temperature with the furnace.
Claims (6)
1. a kind of lithium ion battery negative material preparation method, it is characterised in that the negative electrode material is a kind of zinc selenide-vulcanization
Zinc composite material is prepared by zinc sulphide hollow Nano ball surface selenizing, specifically includes the following steps:
(1) zinc sulphide hollow nano-sphere is prepared:
It measures zinc chloride and thiocarbamide is dissolved in obtained solution A in a certain amount of distilled water, separately weigh appropriate amounts of gelatin and a certain amount of steaming is added
In distilled water, the heating stirring in water-bath stirs 10~30 after mixing two kinds of solution of A, B until Gelatin obtained solution B
Minute, the autoclave high temperature for being transferred to polytetrafluoroethyllining lining is calcined, after cooled to room temperature, by being collected by centrifugation
Then product is washed three times with distilled water and dehydrated alcohol, is dried in 60 DEG C of baking ovens, zinc sulfide nano-sphere is made；
(2) zinc selenide-zinc sulphide composite material is prepared:
It takes the zinc sulphide hollow nano-sphere prepared in step (1) to mix with selenium powder and grinds uniformly, be placed in tube furnace, in argon gas
High-temperature calcination under atmosphere can be prepared by zinc selenide-zinc sulphide composite material after cooling.
2. preparation method according to claim 1, it is characterised in that: zinc chloride needed for preparing solution A in the step (1)
Quality be 0.5~1g, thiocarbamide quality be 1~2g, distilled water volume be 50~100mL；Solution B is prepared in the step (1)
Required gelatin quality is 0.5~1g, and distilled water volume is 50~100mL；The condition of heating and stirring is 60~80 DEG C.
3. preparation method according to claim 2, it is characterised in that: step (1) the high temperature calcination condition is heating
To 100~150 DEG C, and kept for 12~24 hours.
4. preparation method according to claim 1, it is characterised in that: in the step (2) zinc sulphide hollow nano-sphere with
Selenium powder mass ratio is 20~10:1.
5. preparation method according to claim 1, it is characterised in that: step (2) the high temperature calcination condition be 400~
600 DEG C, keep the temperature 3~6h.
6. the lithium ion battery negative material that any one of -5 preparation method is prepared according to claim 1.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110571416A (en) * | 2019-08-19 | 2019-12-13 | 中南大学 | Transition metal selenium-sulfur compound and preparation method thereof |
| CN112018357A (en) * | 2020-08-17 | 2020-12-01 | 五邑大学 | Electrode composite material |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101916854A (en) * | 2010-08-30 | 2010-12-15 | 上海交通大学 | Preparation method of zinc sulfide/carbon composite material for negative electrode of lithium ion battery |
| US20110104570A1 (en) * | 2009-11-04 | 2011-05-05 | Roy Christie Galloway | Cathode compositions comprising zn and chalcogenide and energy storage cell comprising same |
| CN103346201A (en) * | 2013-05-24 | 2013-10-09 | 深圳市亚太兴实业有限公司 | Preparation method of germanium-doped CZTS thin film, thin film and solar cell |
| CN103848456A (en) * | 2012-12-05 | 2014-06-11 | 中国科学院理化技术研究所 | Preparation method of hollow stannic oxide micro-nano particles |
| CN104868102A (en) * | 2015-06-10 | 2015-08-26 | 中南大学 | Sodium ion battery zinc sulfide based negative electrode material and preparation method thereof |
| CN108232142A (en) * | 2017-12-22 | 2018-06-29 | 中国科学院福建物质结构研究所 | A kind of zinc sulphide/graphene composite material, preparation method and application |
| CN108321389A (en) * | 2018-01-16 | 2018-07-24 | 浙江衡远新能源科技有限公司 | A kind of lithium ion battery carbon coating zinc sulfide nano-sphere negative material and preparation method thereof |
| CN108550806A (en) * | 2018-03-28 | 2018-09-18 | 中南大学 | A kind of MnSe/CoSe2Composite material and preparation method and application |
| CN109037617A (en) * | 2018-07-10 | 2018-12-18 | 厦门理工学院 | A kind of cobaltous selenide/nitrogen-doped carbon composite material and preparation method, application |
-
2019
- 2019-03-07 CN CN201910172794.2A patent/CN109768265B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110104570A1 (en) * | 2009-11-04 | 2011-05-05 | Roy Christie Galloway | Cathode compositions comprising zn and chalcogenide and energy storage cell comprising same |
| CN101916854A (en) * | 2010-08-30 | 2010-12-15 | 上海交通大学 | Preparation method of zinc sulfide/carbon composite material for negative electrode of lithium ion battery |
| CN103848456A (en) * | 2012-12-05 | 2014-06-11 | 中国科学院理化技术研究所 | Preparation method of hollow stannic oxide micro-nano particles |
| CN103346201A (en) * | 2013-05-24 | 2013-10-09 | 深圳市亚太兴实业有限公司 | Preparation method of germanium-doped CZTS thin film, thin film and solar cell |
| CN104868102A (en) * | 2015-06-10 | 2015-08-26 | 中南大学 | Sodium ion battery zinc sulfide based negative electrode material and preparation method thereof |
| CN108232142A (en) * | 2017-12-22 | 2018-06-29 | 中国科学院福建物质结构研究所 | A kind of zinc sulphide/graphene composite material, preparation method and application |
| CN108321389A (en) * | 2018-01-16 | 2018-07-24 | 浙江衡远新能源科技有限公司 | A kind of lithium ion battery carbon coating zinc sulfide nano-sphere negative material and preparation method thereof |
| CN108550806A (en) * | 2018-03-28 | 2018-09-18 | 中南大学 | A kind of MnSe/CoSe2Composite material and preparation method and application |
| CN109037617A (en) * | 2018-07-10 | 2018-12-18 | 厦门理工学院 | A kind of cobaltous selenide/nitrogen-doped carbon composite material and preparation method, application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110571416A (en) * | 2019-08-19 | 2019-12-13 | 中南大学 | Transition metal selenium-sulfur compound and preparation method thereof |
| CN112018357A (en) * | 2020-08-17 | 2020-12-01 | 五邑大学 | Electrode composite material |
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