CN103066276B - A kind of preparation method of lithium ion battery cobalt hydroxide carbon compound cathode materials - Google Patents
A kind of preparation method of lithium ion battery cobalt hydroxide carbon compound cathode materials Download PDFInfo
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- CN103066276B CN103066276B CN201210521899.2A CN201210521899A CN103066276B CN 103066276 B CN103066276 B CN 103066276B CN 201210521899 A CN201210521899 A CN 201210521899A CN 103066276 B CN103066276 B CN 103066276B
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Abstract
A kind of lithium ion battery cobalt hydroxide carbon compound cathode materials of the present invention and preparation method thereof：Starch is weighed, the concentrated sulfuric acid, water and template silica, roasting obtain the internal porous CNT for nano hollow carbon pipe；After being flowed back with the concentrated sulfuric acid, it is added in glycol water, then cobalt oxalate, sodium acid carbonate and potassium borate regulation pH value, hydro-thermal reaction obtains the porous carbon nano tube compound material of cobalt hydroxide；Mix, mixed well with isopropanol with acetylene black, hydroxymethyl cellulose and water, obtain composite negative pole material.The preparation method technique of the present invention is relatively also relatively simple, the porous carbon nano tube compound material of cobalt hydroxide of preparation, by the way that cobalt hydroxide is evenly distributed on inside and outside porous CNT, so that the Stability Analysis of Structures of composite and being uniformly dispersed, therefore possessing outside high energy density, also with stable cycle performance, during as lithium ion battery negative material, specific capacity is high, and service life is long.
Description
Technical field
The present invention relates to a kind of preparation method of lithium ion battery, more particularly to a kind of lithium ion battery cobalt hydroxide-carbon
Composite negative pole material and preparation method thereof.
Background technology
Electronic apparatus miniaturization, energetic, the trend of portability, the development of space technology and the demand of defence equipment and
The development and exploitation of electric automobile, have higher requirement to the performance of lithium ion battery.
The improvement of performance of lithium ion battery depends primarily on the raising of embedding lithium electrode material energy densities and cycle life, mesh
The lithium ion battery of preceding commercialization mostly using lithium transition-metal oxide/graphite system as negative active core-shell material as lithium from
Sub- cell negative electrode material, CoO theoretical specific capacity is up to 715mAh/g, about the 2 of graphitized carbon material times.
Although the CoO in report has higher specific capacity, efficiency and cycle performance are poor first for it.Cobalt hydroxide
It has been used widely in Ni-MH battery, it has also been widely studied as the presoma of lithium ion battery electrode material
And synthesis, but be oxide (CoO or the Co for being sintered into cobalt3O4), it could make as lithium ion battery electrode material
With, used process route complex steps, and it is larger to consume energy.
The content of the invention
To overcome above mentioned problem, the present invention provides a kind of preparation of cobalt hydroxide-carbon composite cathode material of lithium ion battery
Method, when the anode material prepared using this method is used for lithium ion battery, while with larger specific capacity, knot
Structure is stable, good cycle.
To achieve these goals, a kind of cobalt hydroxide-carbon composite cathode material of lithium ion battery that the present invention is provided
Preparation method, comprises the following steps：
Step 1, porous CNT is prepared
According to weight than 1: (0.1-0.15): (1-10): (0.5-2) weighs starch, the concentrated sulfuric acid, water and template titanium dioxide
Silicon, mixing, mixture is dried, and mixture is put into the pyroreaction kettle of inert gas shielding and is calcined, pyroreaction kettle
Heating rate is heats up 50-80 DEG C per hour, and temperature rises to 500-700 DEG C, is kept for 4-7 hours, removes template agent removing silica,
Obtain the internal porous CNT for nano hollow carbon pipe；
Step 2, cobalt hydroxide-porous carbon nano tube compound material
Above-mentioned porous CNT is flowed back 1-2 hours for 60-80 DEG C with the concentrated sulfuric acid；
Then the 2-5 parts of porous CNTs flowed back are added in 10-200 parts of Glycol Mixture, second two
The volume ratio of ethylene glycol and water in alcohol-water solution is 1: 10-1: 1, then at room temperature ultrasonic disperse 3-6 hours；Then press
Parts by weight, add 2-8 parts of cobalt oxalates, 0.5-1 parts of sodium acid carbonates and 0.2-0.5 parts of potassium borates, and regulation pH value is 10-13, stirring
Fall back in hot kettle, seal, and hydro-thermal reaction 8-24 hours at 100-200 DEG C, obtain cobalt hydroxide-porous CNT
Composite；
Step 3, composite negative pole material is prepared
The cobalt hydroxide-porous carbon nano tube compound material, acetylene black, hydroxymethyl cellulose (CMC) and water are mixed,
Wherein, the mixed proportion of the cobalt hydroxide-porous carbon nano tube compound material, acetylene black, CMC and water is (10-20): (3-
5): (2-3): (50-80), the mixture being mixed to get is mixed well with isopropanol, composite negative pole material is obtained.
Wherein, stirring 3-6 hours before mixture is dried in step 1.
Wherein, drying is described in step 1：Heating rate is heats up 10-20 DEG C per hour, and temperature rises to 150-200 DEG C,
Kept for 3-8 hours.
Wherein, in step 1, the method for removing template agent removing silica is：Mixture after roasting is put into potassium hydroxide
Middle stirring 10-15 hours, dissolves silica template, then filters, washs, dries.
Present invention also offers cobalt hydroxide-carbon composite cathode material of lithium ion battery prepared by a kind of above method.
Cobalt hydroxide prepared by the present invention-porous carbon nano tube compound material is more by the way that cobalt hydroxide is evenly distributed on
Inside and outside the CNT of hole so that the Stability Analysis of Structures of composite and be uniformly dispersed, therefore possessing outside high energy density, also
With stable cycle performance, during as lithium ion battery negative material, specific capacity is high, and service life is long.In addition, the present invention
Preparation method technique is relatively also relatively simple.
Embodiment
Embodiment one
Prepare porous CNT
Starch, the concentrated sulfuric acid and water and template silica are weighed than 1: 0.15: 10: 2 according to weight, is uniformly stirred after mixing
Mix 6 hours, mixture is put into baking oven, baking oven heating rate is heats up 20 DEG C per hour, and temperature rises to 200 DEG C, and holding 3 is small
When, after solvent evaporation, mixture is put into the pyroreaction kettle of inert gas shielding and be calcined, pyroreaction kettle heating rate
To heat up per hour 80 DEG C, temperature rises to 700 DEG C, is kept for 4 hours, the mixture after roasting is put into potassium hydroxide and stirs 15
Hour, silica template is dissolved, then filters, wash, dry, the internal porous carbon nanometer for nano hollow carbon pipe is obtained
Pipe；
Cobalt hydroxide-porous carbon nano tube compound material
Above-mentioned porous CNT is flowed back 1 hour for 80 DEG C with the concentrated sulfuric acid；Then the porous CNT 5 parts flowed back
Add in 200 parts of Glycol Mixture, the volume ratio of ethylene glycol and water in Glycol Mixture is 1: 1, Ran Hou
Ultrasonic disperse 6 hours, then by weight, add 8 parts of cobalt oxalates, 1 part of sodium acid carbonate and 0.5 part of potassium borate, regulation at room temperature
PH value is 13, and stirring is fallen back in hot kettle, sealing, and reaction is filtered after 8 hours, washs, dries at 200 DEG C, is obtained
To cobalt hydroxide-porous carbon nano tube compound material.
Prepare composite negative pole material
The cobalt hydroxide-porous carbon nano tube compound material, acetylene black, CMC and water are mixed, wherein, the hydrogen-oxygen
It can be 20: 5: 3: 80 to change cobalt-porous carbon nano tube compound material, acetylene black, the mixed proportion of CMC and water, with isopropanol by institute
State the mixture being mixed to get to mix well, obtain composite negative pole material.
Embodiment two
Prepare porous CNT
Starch, the concentrated sulfuric acid and water and template silica are weighed than 1: 0.1: 1: 0.5 according to weight, is uniformly stirred after mixing
Mix 3 hours, mixture is put into baking oven, baking oven heating rate is heats up 10 DEG C per hour, and temperature rises to 150 DEG C, and holding 8 is small
When, after solvent evaporation, mixture is put into the pyroreaction kettle of inert gas shielding and be calcined, pyroreaction kettle heating rate
To heat up per hour 50 DEG C, temperature rises to 500 DEG C, is kept for 7 hours, the mixture after roasting is put into potassium hydroxide and stirs 10
Hour, silica template is dissolved, then filters, wash, dry, the internal porous carbon nanometer for nano hollow carbon pipe is obtained
Pipe；
Cobalt hydroxide-porous carbon nano tube compound material
Above-mentioned porous CNT is flowed back 2 hours for 60 DEG C with the concentrated sulfuric acid；Then the porous CNT 2 parts flowed back
Add in 10 parts of Glycol Mixture, the volume ratio of ethylene glycol and water in Glycol Mixture is 1: 1, then in room
The lower ultrasonic disperse of temperature 6 hours, then by weight, adds 2 parts of cobalt oxalates, 0.5 part of sodium acid carbonate and 0.2 part of potassium borate, regulation
PH value is 10, and stirring is fallen back in hot kettle, sealing, and reaction is filtered after 8 hours, washs, dries at 100 DEG C, is obtained
To cobalt hydroxide-porous carbon nano tube compound material.
Prepare composite negative pole material
The cobalt hydroxide-porous carbon nano tube compound material, acetylene black, CMC and water are mixed, wherein, the hydrogen-oxygen
It can be 10: 3: 2: 50 to change cobalt-porous carbon nano tube compound material, acetylene black, the mixed proportion of CMC and water, with isopropanol by institute
State the mixture being mixed to get to mix well, obtain composite negative pole material.
Comparative example
0.5 gram of graphite oxide is dispersed in 300ml isopropanol-water solutions (volume ratio is 1: 10), 6 are stirred at room temperature
Hour, 3.26 grams of cabaltous nitrate hexahydrates are added, 15 milliliters of ammoniacal liquor, 0.08 gram of sodium borohydride, stirring is fallen back in hot kettle, close
Envelope, and reaction is filtered after 5 hours, washs, dries at one hundred and twenty degrees centigrade, obtains graphite oxide-cobalt hydroxide composite wood
Material, it is handled 2 hours for 300 degrees Celsius under nitrogen protection, graphene nanometer sheet-cobaltous oxide composite negative electrode material is obtained.
The cobalt hydroxide-porous carbon nano tube compound material, acetylene black, CMC and water are mixed, wherein, the cobalt hydroxide-porous
Carbon nano tube compound material, acetylene black, the mixed proportion of CMC and water can be 10: 3: 2: 50, be mixed to get with isopropanol by described
Mixture mix well, obtain composite negative pole material.
Using a diameter of 18 millimeters, metal lithium sheet that weight is 0.4 gram as positive active material, using modified polypropene barrier film as
Barrier film, with the LiPF of 1 mol/L6Solution (solvent is EC: DMC mixed solvent of volume ratio 1: 1) is electrolyte, respectively with
It is negative material that 0.05 gram is made product by above-described embodiment one, two and comparative example, is equably coated on copper mesh and does negative pole, is made
Into 2016 type button cells.Electric performance test is carried out in the case where test temperature is 25 DEG C, after tested the material of the embodiment one and two
Material is compared with the material of comparative example, and first discharge specific capacity improves more than 35-45%, and cycle life improves more than 2 times.
The specific embodiment of the present invention is described in detail above, but it is intended only as example, and the present invention is not limited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
Substitute also all among scope of the invention.Therefore, the impartial conversion made without departing from the spirit and scope of the invention and
Modification, all should be contained within the scope of the invention.
Claims (5)
1. a kind of preparation method of cobalt hydroxide-carbon composite cathode material of lithium ion battery, it is characterised in that including following step
Suddenly：
Step 1, porous CNT is prepared
According to weight than 1: (0.1-0.15): (1-10): (0.5-2) weighs starch, the concentrated sulfuric acid, water and template silica,
Mixing, mixture is dried, and mixture is put into the pyroreaction kettle of inert gas shielding and is calcined, pyroreaction kettle heating
Speed is heats up 50-80 DEG C per hour, and temperature rises to 500-700 DEG C, is kept for 4-7 hours, removes template agent removing silica, obtain
Inside is the porous CNT of nano hollow carbon pipe；
Step 2, cobalt hydroxide-porous carbon nano tube compound material
Above-mentioned porous CNT is flowed back 1-2 hours for 60-80 DEG C with the concentrated sulfuric acid；
Then the 2-5 parts of porous CNTs flowed back are added in 10-200 parts of Glycol Mixture, ethylene glycol-water
The volume ratio of ethylene glycol and water in solution is 1: 10-1: 1, then at room temperature ultrasonic disperse 3-6 hours；Then by weight
Part, 2-8 parts of cobalt oxalates, 0.5-1 parts of sodium acid carbonates and 0.2-0.5 parts of potassium borates are added, regulation pH value is 10-13, is fallen after stirring
Enter in water heating kettle, seal, and hydro-thermal reaction 8-24 hours at 100-200 DEG C, obtain cobalt hydroxide-porous CNT and be combined
Material；
Step 3, composite negative pole material is prepared
The cobalt hydroxide-porous carbon nano tube compound material, acetylene black, CMC and water are mixed, wherein, the cobalt hydroxide-
Porous carbon nano tube compound material, acetylene black, the mixed proportion of CMC and water are (10-20): (3-5): (2-3): (50-80), are used
Isopropanol mixes well the mixture being mixed to get, and obtains composite negative pole material.
2. according to the method described in claim 1, it is characterised in that stirring 3-6 hours before mixture is dried in step 1.
3. method according to claim 1 or 2, it is characterised in that drying described in step 1 is：Heating rate is per small
Shi Shengwen 10-20 DEG C, temperature rises to 150-200 DEG C, is kept for 3-8 hours.
4. the method for according to the method described in claim 1, it is characterised in that in step 1, removing template agent removing silica is：
Mixture after roasting is put into potassium hydroxide and stirred 10-15 hours, silica template is dissolved, then filter, wash,
Dry.
5. cobalt hydroxide-carbon composite cathode material of lithium ion battery prepared by a kind of method as claimed in claim 1.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106129425A (en) * | 2016-09-21 | 2016-11-16 | 许昌学院 | A kind of porous carbon electrode material and its preparation method and application |
| CN106206060A (en) * | 2016-09-25 | 2016-12-07 | 桂林理工大学 | The preparation of cobalt hydroxide@carbon fiber nanometer composite material and electrode material for super capacitor application |
| CN109411732A (en) * | 2018-11-05 | 2019-03-01 | 桑顿新能源科技有限公司 | A kind of preparation method of the nucleocapsid cladding compound lithium sulfur battery anode material of sulphur-carbon nanotube |
| CN111200119B (en) * | 2018-11-19 | 2021-01-29 | 河南科技学院 | SiO (silicon dioxide)2/CoO/graphene composite negative electrode material and preparation method thereof |
| CN113663672B (en) * | 2020-05-15 | 2023-08-15 | 香港城市大学深圳研究院 | Cobalt oxide photocatalytic material with high photoelectrocatalytic activity and preparation method thereof |
| CN114272945B (en) * | 2020-10-13 | 2023-07-18 | 天津大学 | Metal organic framework derived carbon grown cobalt hydroxide and preparation method thereof |
| CN116354351B (en) * | 2023-03-21 | 2023-10-27 | 中国丝绸博物馆 | Preparation method and application of energy-saving micro-environment humidity automatic regulating material |
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