CN107706397A - Nickel-cobalt-manganese ternary combination electrode material of modified carbon nano-tube modification and preparation method thereof - Google Patents
Nickel-cobalt-manganese ternary combination electrode material of modified carbon nano-tube modification and preparation method thereof Download PDFInfo
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- CN107706397A CN107706397A CN201711069045.4A CN201711069045A CN107706397A CN 107706397 A CN107706397 A CN 107706397A CN 201711069045 A CN201711069045 A CN 201711069045A CN 107706397 A CN107706397 A CN 107706397A
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- 239000007772 electrode material Substances 0.000 title claims abstract description 64
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 230000004048 modification Effects 0.000 title claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000002715 modification method Methods 0.000 title description 2
- 238000012986 modification Methods 0.000 claims abstract description 44
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 42
- -1 nitrogen modified carbon nano-tube Chemical class 0.000 claims abstract description 40
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052796 boron Inorganic materials 0.000 claims abstract description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 29
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 22
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims description 29
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 24
- 229920000877 Melamine resin Polymers 0.000 claims description 18
- 239000004327 boric acid Substances 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 14
- 239000000725 suspension Substances 0.000 claims description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 11
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 9
- 238000005245 sintering Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 125000005619 boric acid group Chemical group 0.000 claims description 4
- 239000002071 nanotube Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910006525 α-NaFeO2 Inorganic materials 0.000 claims description 2
- 229910006596 α−NaFeO2 Inorganic materials 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- 239000002041 carbon nanotube Substances 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 13
- 125000005909 ethyl alcohol group Chemical group 0.000 description 11
- 230000014759 maintenance of location Effects 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 229910021393 carbon nanotube Inorganic materials 0.000 description 7
- 150000007974 melamines Chemical class 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 235000002908 manganese Nutrition 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 235000013495 cobalt Nutrition 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- DZVPMKQTULWACF-UHFFFAOYSA-N [B].[C].[N] Chemical compound [B].[C].[N] DZVPMKQTULWACF-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to a kind of nickel-cobalt-manganese ternary combination electrode material based on the modification of modified Nano pipe, it is made by modified carbon nano-tube and presoma；The modified carbon nano-tube includes one or both of nitrogen modified carbon nano-tube or boron modification CNT；The modified carbon nano-tube accounts for 1% the 10% of combination electrode material quality；The presoma includes lithium carbonate and nickel cobalt manganese, and the mol ratio of elemental lithium and nickel cobalt manganese in the lithium carbonate is 1.0 1.05: 1.Invention also provides the preparation method of above-mentioned combination electrode material.The present invention can improve the problems such as electronic conductivity is low, multiplying power stability is poor, high voltage cycle stability difference.
Description
Technical field
A kind of battery material technical field of the present invention, and in particular to nickel-cobalt-manganese ternary positive pole based on the modification of modified Nano pipe
The preparation method of material.
Background technology
Ternary anode material for lithium-ion batteries is a kind of Olivine-type Cathode Material in Li-ion Batteries developed in recent years, have into
The advantages that this moderate, high power capacity, high circulation stability.Ternary material, and cobalt acid lithium material compare, and reduce production cost, carry
High security performance, being compared with lithium manganate material has higher stability, and the status in positive electrode progressively shows, not
Come electric car, electrokinetic cell field, ternary material would is that favourable competitor.
Compared with cobalt acid lithium, ternary material there is also some urgent problems, mainly include electronic conductivity it is low, times
Rate stability is poor, high voltage cycle stability difference etc., wants to realize its large-scale production, it is necessary to solve these problems.
The content of the invention
It is an object of the invention to provide a kind of carbon nano tube modified nickel-cobalt-manganese ternary combination electrode material of synthesis modification and
Its preparation method, the decorative material can improve that electronic conductivity is low, multiplying power stability is poor, high voltage cycle stability is poor
The problems such as.
The present invention adopts the following technical scheme that：
A kind of nickel-cobalt-manganese ternary combination electrode material of modified Nano pipe modification, it is made by modified carbon nano-tube and presoma；
The modified carbon nano-tube includes one or both of nitrogen modified carbon nano-tube and boron modification CNT；The carbon modified is received
Mitron accounts for the 1%-10% of combination electrode material quality；The presoma includes lithium carbonate and nickel cobalt manganese, the lithium in the lithium carbonate
The mol ratio of element and nickel cobalt manganese is 1.0-1.05: 1.
Further, the modified carbon nano-tube accounts for the 1%-5% of combination electrode material quality.
More excellent, the modified carbon nano-tube accounts for the 5% of combination electrode material quality.
Further, the nickel-cobalt-manganese ternary combination electrode material is α-NaFeO2Layer structure.
Further, the modified carbon nano-tube is nitrogen modified carbon nano-tube；The nitrogen source of the nitrogen modified carbon nano-tube is
Melamine；The mass ratio of nitrogen and CNT in the melamine is：0.04-0.06∶0.94-0.96.
Further, the modified carbon nano-tube is boron modification CNT；The boron source of the boron modification CNT is
Boric acid；The mass ratio of boron element and CNT in the boric acid is：0.04-0.06∶0.94-0.96.
Further, the modified carbon nano-tube is nitrogen modified carbon nano-tube and boron modification CNT；The nitrogen is modified
The nitrogen source of CNT is melamine；The boron source of the boron modification CNT is boric acid；Nitrogen member in the melamine
Element, the mass ratio of the boron element in boric acid and CNT are：0.02-0.03∶0.02-0.03∶0.94-0.96.
A kind of preparation method of above-mentioned nickel-cobalt-manganese ternary combination electrode material, it comprises the following steps：
（1）CNT, melamine and/or boric acid are mixed in mass ratio, ball milling, obtain modified carbon nano-tube presoma,
Modified carbon nano-tube presoma is placed in nitrogen atmosphere and is calcined, sintering temperature is 400 DEG C -600 DEG C, roasting time 4-8
H, obtain modified carbon nano-tube；
（2）Lithium carbonate, nickel cobalt manganese material precursor are mixed in proportion, is added in absolute ethyl alcohol and is disperseed；Preferably, institute
The mol ratio for stating the elemental lithium in lithium carbonate and nickel cobalt manganese is 1.02: 1；
（3）By modified carbon nano-tube in positive electrode proportion, weigh modified carbon nano-tube and be placed in step（2）Described in
In ethanol, fully dispersed, ball milling, suspension is obtained；
（4）By step（3）Middle suspension is put in evaporating water in baking oven, obtains and dries presoma；
（5）By step（4）In drying presoma be placed in nitrogen atmosphere batch-type furnace and be sintered, sintering temperature is 700 DEG C-
900 DEG C, sintering time 12-24h, obtain the nickel-cobalt-manganese ternary combination electrode material of modified carbon nano-tube modification.
In preparation method, the step（2）The concentration of middle ethanol is 99.5%.
In preparation method, the step（3）Middle Ball-milling Time is 4-6 hours.
Preferably, the step（3）Middle Ball-milling Time is 4 hours.
In preparation method, step（4）In drying condition be 60-80 DEG C of temperature, the time is 8-14 hours.
Preferably, step（4）In drying condition be 70 DEG C of temperature, the time is 12 hours.
Preferably, step（5）In, it is sintered in nitrogen atmosphere batch-type furnace, sintering temperature is 800 DEG C, sintering time
12h, heating rate are 3 ~ 8 DEG C/min, and preferably heating rate is 5 DEG C/min.
In preparation method, the step（2）The mol ratio of elemental lithium and nickel cobalt manganese in middle lithium carbonate is more than 1；Preferably
1.01-1.05∶1。
In preparation method, the step（3）The content of middle nitrogen, boron in combination electrode material is by modified carbon nano-tube at it
In weight/mass percentage composition determine.
The beneficial effects of the present invention are：
（1）With more or less cumbersome there is building-up process during existing modified carbon nano-tube synthetic method, the reaction time
It is long to even relate to the use of strong acid, therefore larger limitation is received in actual applications.The carbon modified of this patent synthesis is received
Mitron is using melamine, boric acid, CNT as raw material, and using ball milling, the method for roasting is simple with synthesis technique, significantly
Combined coefficient is improved, and advantages of nontoxic raw materials is harmless, synthetic method is environmentally protective, it is easy to accomplish industrialization.
（2）The preparation method that the technique that electrode material synthesis is burnt till using ball milling mixing and high temperature is combined, simple process,
Cost is low, is adapted to large-scale production.
（3）The electrode material modified using modified carbon nano-tube can significantly improve the electric conductivity of electrode material, improve electricity
The high rate performance and cyclical stability of pole material.
（4）To those skilled in the art, although the amount for improving modified carbon nano-tube can improve the conduction of material
Property, transfer rate of the electronics in electrode material is improved, but inventor has found in research process, too many modified carbon nano-tube
Modification can also weaken its chemical property, therefore, modified carbon nano-tube of the present invention to a certain extent（Nitrogen, boron）In combination electrode
Shared mass ratio is 1%-10%, preferably 1%-5%, more preferably 5% in material.
（5）Modified carbon nano-tube is one or two kinds of element combinations, and being mainly in view of doping nonmetalloid can increase
The surface defect of CNT, and then the electric conductivity of electrode material can be improved, so as to reach the stability of raising material and follow
The purpose of ring performance.
Embodiment
The present invention is specifically described and illustrated below by embodiment.
Comparative example 1
Weigh 9.22g nickel cobalt manganese presomas, 3.8g lithium carbonates are put in ball grinder, add 50 ml absolute ethyl alcohols it is fully dispersed,
Ball milling obtains finely dispersed solution in 4 hours, and above-mentioned solution is placed in 70 DEG C of baking ovens and dried, it is compound to obtain dry nickel cobalt manganese
Electrode material presoma.This presoma is placed in batch-type furnace, calcined at 800 DEG C 12 hours, heating rate is 5 DEG C/min,
Unmodified nickel cobalt manganese electrode material is prepared, under 1C discharge-rates, first discharge specific capacity is reached for 120 mAh/g,
Capability retention is 70% after circulating 100 times.
Comparative example 2
9.22g nickel cobalt manganese presomas are weighed, 3.8g lithium carbonates are put in ball grinder, 50 ml absolute ethyl alcohols are added, then upper
State addition 0.651g CNTs in suspension.By above-mentioned solution is fully dispersed, ball milling obtains finely dispersed solution in 4 hours,
Above-mentioned solution is placed in 70 DEG C of baking ovens and dried, obtains the carbon nano tube modified nickel cobalt manganese combination electrode material forerunner of drying
Body.This presoma is placed in batch-type furnace, calcined at lower 800 DEG C of nitrogen atmosphere 12 hours, heating rate is 5 DEG C/min, system
It is standby to obtain the modification nickel cobalt manganese combination electrode material that carbon nanotube mass percentage composition is 5%.This combination electrode material is assembled into
Button cell carries out charge-discharge test, and under 1C discharge-rates, first discharge specific capacity reaches 131mAh/g, after circulating 100 times,
Capability retention is 78%.
Embodiment 1
1 g CNTs are weighed, 0.075g melamines, are put into ball grinder, ball milling 4 hours, are then put said mixture
In the batch-type furnace of nitrogen atmosphere protection, 500 DEG C are calcined 6 hours, obtain nitrogen modified carbon nano-tube.Then 9.22g nickel cobalts are weighed
Manganese presoma, 3.8g lithium carbonates are put in ball grinder, add 50 ml absolute ethyl alcohols, and nitrogen is then added in above-mentioned suspension changes
Property CNT 0.651g.By above-mentioned solution is fully dispersed, ball milling obtains finely dispersed solution in 4 hours, above-mentioned solution is put
Dried 12 hours in 70 DEG C of baking ovens, obtain the nickel cobalt manganese combination electrode material forerunner of dry nitrogen modified carbon nano-tube modification
Body.This presoma is placed in batch-type furnace, calcined at lower 800 DEG C of nitrogen atmosphere 12 hours, heating rate is 5 DEG C/min, system
It is standby to obtain the modification nickel cobalt manganese combination electrode material that nitrogen modified carbon nano-tube weight/mass percentage composition is 5%.By this combination electrode material
It is assembled into button cell and carries out charge-discharge test, under 1C discharge-rates, first discharge specific capacity reaches 140mAh/g, circulation
After 100 times, capability retention 83%.
Embodiment 2
1 g CNTs are weighed, 0.06g melamines, are put into ball grinder, ball milling 4 hours, are then placed in said mixture
In the batch-type furnace of nitrogen atmosphere protection, 400 DEG C are calcined 4 hours, obtain nitrogen modified carbon nano-tube.Then 9.22g nickel cobalt manganeses are weighed
Presoma, 3.88g lithium carbonates are put in ball grinder, add 50 ml absolute ethyl alcohols, and nitrogen is then added in above-mentioned suspension is modified
CNT 0.131g.By above-mentioned solution is fully dispersed, ball milling obtains finely dispersed solution in 5 hours, above-mentioned solution is placed in
Dried 14 hours in 60 DEG C of baking ovens, obtain the nickel cobalt manganese combination electrode material presoma of dry nitrogen modified carbon nano-tube modification.
This presoma is placed in batch-type furnace, calcined at lower 700 DEG C of nitrogen atmosphere 24 hours, heating rate is 4 DEG C/min, is prepared
Obtain the modification nickel cobalt manganese combination electrode material that nitrogen modified carbon nano-tube weight/mass percentage composition is 1%.By this combination electrode material group
Dress up button cell and carry out charge-discharge test, under 1C discharge-rates, first discharge specific capacity reaches 139mAh/g, circulation 100
After secondary, capability retention 82%.
Embodiment 3
1 g CNTs are weighed, 0.2862g boric acid, are put into ball grinder, ball milling 4 hours, said mixture are then placed in nitrogen
Atmosphere is enclosed in the batch-type furnace of protection, and 500 DEG C are calcined 6 hours, obtain boron modification CNT.Then before weighing 9.22g nickel cobalt manganeses
Body is driven, 3.8g lithium carbonates are put in ball grinder, add 50 ml absolute ethyl alcohols, and boron modification carbon is then added in above-mentioned suspension
Nanotube 0.651g.By above-mentioned solution is fully dispersed, ball milling obtains finely dispersed solution in 4 hours, above-mentioned solution is placed in 70
Dried in DEG C baking oven, obtain the carbon nano tube modified nickel cobalt manganese combination electrode material presoma of dry boron modification.By this forerunner
Body is placed in batch-type furnace, is calcined at lower 800 DEG C of nitrogen atmosphere 12 hours, and heating rate is 5 DEG C/min, and boron is prepared and changes
Property carbon nanotube mass percentage composition be 5% modification nickel cobalt manganese combination electrode material.This combination electrode material is assembled into button
Battery carries out charge-discharge test, and under 1C discharge-rates, first discharge specific capacity reaches 144mAh/g, after circulating 100 times, capacity
Conservation rate is 85%.
Embodiment 4
1 g CNTs are weighed, 0.3429g boric acid, are put into ball grinder, ball milling 4 hours, said mixture are then placed in nitrogen
Atmosphere is enclosed in the batch-type furnace of protection, and 600 DEG C are calcined 8 hours, obtain boron modification CNT.Then before weighing 9.22g nickel cobalt manganeses
Body is driven, 3.73g lithium carbonates are put in ball grinder, add 50 ml absolute ethyl alcohols, and boron modification carbon is then added in above-mentioned suspension
Nanotube 1.295g.By above-mentioned solution is fully dispersed, ball milling obtains finely dispersed solution in 6 hours, above-mentioned solution is placed in 80
Dried 8 hours in DEG C baking oven, obtain the carbon nano tube modified nickel cobalt manganese combination electrode material presoma of dry boron modification.By this
Presoma is placed in batch-type furnace, is calcined at lower 900 DEG C of nitrogen atmosphere 18 hours, and heating rate is 6 DEG C/min, is prepared
Boron modification carbon nanotube mass percentage composition is 10% modification nickel cobalt manganese combination electrode material.This combination electrode material is assembled
Charge-discharge test is carried out into button cell, under 1C discharge-rates, first discharge specific capacity reaches 153mAh/g, circulates 100 times
Afterwards, capability retention 86%.
Embodiment 5
1 g CNTs, 0.1431g boric acid and 0.0375g melamines are weighed, is put into ball grinder, ball milling 4 hours, so
Said mixture is placed in the batch-type furnace of nitrogen atmosphere protection afterwards, 500 DEG C are calcined 6 hours, obtain boron nitrogen modified carbon nano-tube.
Then 9.22g nickel cobalt manganese presomas are weighed, 3.8g lithium carbonates are put in ball grinder, 50 ml absolute ethyl alcohols are added, then upper
State and boron nitrogen modified carbon nano-tube 0.3906g is added in suspension.By above-mentioned solution is fully dispersed, ball milling obtain within 4 hours it is scattered equal
Even solution, above-mentioned solution is placed in 70 DEG C of baking ovens and dried, obtain the nickel cobalt manganese of dry boron nitrogen modified carbon nano-tube modification
Combination electrode material presoma.This presoma is placed in batch-type furnace, calcined at lower 800 DEG C of nitrogen atmosphere 12 hours, heating
Speed is 5 DEG C/min, and the modification nickel cobalt manganese combination electrode material that boron nitrogen modified carbon nano-tube weight/mass percentage composition is 3% is prepared
Material.This combination electrode material is assembled into button cell and carries out charge-discharge test, under 1C discharge-rates, first discharge specific capacity
Reach 151mAh/g, after circulating 100 times, capability retention 89%.
Embodiment 6
1 g CNTs, 0.1431g boric acid and 0.0375g melamines are weighed, is put into ball grinder, ball milling 4 hours, so
Said mixture is placed in the batch-type furnace of nitrogen atmosphere protection afterwards, 500 DEG C are calcined 6 hours, obtain boron nitrogen modified carbon nano-tube.
Then 9.22g nickel cobalt manganese presomas are weighed, 3.8g lithium carbonates are put in ball grinder, 50 ml absolute ethyl alcohols are added, then upper
State and boron nitrogen modified carbon nano-tube 0.651g is added in suspension.By above-mentioned solution is fully dispersed, ball milling is uniformly dispersed for 4 hours
Solution, above-mentioned solution is placed in 70 DEG C of baking ovens and dried, the nickel cobalt manganese for obtaining dry boron nitrogen modified carbon nano-tube modification is answered
Composite electrode material precursor.This presoma is placed in batch-type furnace, calcined at lower 800 DEG C of nitrogen atmosphere 12 hours, heating speed
Rate is 5 DEG C/min, and the modification nickel cobalt manganese combination electrode material that boron nitrogen modified carbon nano-tube weight/mass percentage composition is 5% is prepared
Material.This combination electrode material is assembled into button cell and carries out charge-discharge test, under 1C discharge-rates, first discharge specific capacity
Reach 165mAh/g, after circulating 100 times, capability retention 94%.
Embodiment 7
1 g CNTs, 0.1143g boric acid and 0.0300g melamines are weighed, is put into ball grinder, ball milling 4 hours, so
Said mixture is placed in the batch-type furnace of nitrogen atmosphere protection afterwards, 500 DEG C are calcined 6 hours, obtain boron nitrogen modified carbon nano-tube.
Then 9.22g nickel cobalt manganese presomas are weighed, 3.8g lithium carbonates are put in ball grinder, 50 ml absolute ethyl alcohols are added, then upper
State and boron nitrogen modified carbon nano-tube 0.651g is added in suspension.By above-mentioned solution is fully dispersed, ball milling is uniformly dispersed for 4 hours
Solution, above-mentioned solution is placed in 70 DEG C of baking ovens and dried, the nickel cobalt manganese for obtaining dry boron nitrogen modified carbon nano-tube modification is answered
Composite electrode material precursor.This presoma is placed in batch-type furnace, calcined at lower 800 DEG C of nitrogen atmosphere 12 hours, heating speed
Rate is 5 DEG C/min, and the modification nickel cobalt manganese combination electrode material that boron nitrogen modified carbon nano-tube weight/mass percentage composition is 5% is prepared
Material.This combination electrode material is assembled into button cell and carries out charge-discharge test, under 1C discharge-rates, first discharge specific capacity
Reach 160mAh/g, after circulating 100 times, capability retention 94%.
Embodiment 8
1 g CNTs, 0.1431g boric acid and 0.0375g melamines are weighed, is put into ball grinder, ball milling 4 hours, so
Said mixture is placed in the batch-type furnace of nitrogen atmosphere protection afterwards, 500 DEG C are calcined 6 hours, obtain boron nitrogen modified carbon nano-tube.
Then 9.22g nickel cobalt manganese presomas are weighed, 3.8g lithium carbonates are put in ball grinder, 50 ml absolute ethyl alcohols are added, then upper
State and boron nitrogen modified carbon nano-tube 1.0416g is added in suspension.By above-mentioned solution is fully dispersed, ball milling obtain within 4 hours it is scattered equal
Even solution, above-mentioned solution is placed in 70 DEG C of baking ovens and dried, obtain the nickel cobalt manganese of dry boron nitrogen modified carbon nano-tube modification
Combination electrode material presoma.This presoma is placed in batch-type furnace, calcined at lower 800 DEG C of nitrogen atmosphere 12 hours, heating
Speed is 5 DEG C/min, and the modification nickel cobalt manganese combination electrode material that boron nitrogen modified carbon nano-tube weight/mass percentage composition is 8% is prepared
Material.This combination electrode material is assembled into button cell and carries out charge-discharge test, under 1C discharge-rates, first discharge specific capacity
Reach 156mAh/g, after circulating 100 times, capability retention 91%.
Embodiment 9
1 g CNTs, 0.1714g boric acid and 0.0450g melamines are weighed, is put into ball grinder, ball milling 4 hours, so
Said mixture is placed in the batch-type furnace of nitrogen atmosphere protection afterwards, 500 DEG C are calcined 6 hours, obtain boron nitrogen modified carbon nano-tube.
Then 9.22g nickel cobalt manganese presomas are weighed, 3.8g lithium carbonates are put in ball grinder, 50 ml absolute ethyl alcohols are added, then upper
State and boron nitrogen modified carbon nano-tube 0.651g is added in suspension.By above-mentioned solution is fully dispersed, ball milling is uniformly dispersed for 4 hours
Solution, above-mentioned solution is placed in 70 DEG C of baking ovens and dried, the nickel cobalt manganese for obtaining dry boron nitrogen modified carbon nano-tube modification is answered
Composite electrode material precursor.This presoma is placed in batch-type furnace, calcined at lower 800 DEG C of nitrogen atmosphere 12 hours, heating speed
Rate is 5 DEG C/min, and the modification nickel cobalt manganese combination electrode material that boron nitrogen modified carbon nano-tube weight/mass percentage composition is 5% is prepared
Material.This combination electrode material is assembled into button cell and carries out charge-discharge test, under 1C discharge-rates, first discharge specific capacity
Reach 158mAh/g, after circulating 100 times, capability retention 93%.
From above experimental data, the technique being combined by surface modification with high temperature sintering, received with boron nitrogen carbon modified
For mitron as face finish material, the combination electrode material being prepared has excellent chemical property；1C discharge-rates
Under, first discharge specific capacity up to arrives 165mAh/g, and after circulating 100 times, the capability retention of combination electrode material is 94%,
It is substantially better than no modified electrode material（Comparative example 1）With it is unmodified carbon nano tube modified（Comparative example 2）Electrode material.
Embodiment described above is only that the preferred embodiment of the present invention is described, but is not limited to this, this
The technical staff in field is easy to understand according to above-described embodiment the spirit of the present invention, and makes different amplification and change, but
Without departing from the spirit of the present invention, all within protection scope of the present invention.
Claims (10)
1. a kind of nickel-cobalt-manganese ternary combination electrode material of modified Nano pipe modification, it is characterised in that it is by modified carbon nano-tube
It is made with presoma；The modified carbon nano-tube includes nitrogen modified carbon nano-tube and one kind in boron modification CNT or two
Kind；The modified carbon nano-tube accounts for the 1%-10% of combination electrode material quality；The presoma includes lithium carbonate and nickel cobalt manganese, institute
The mol ratio for stating the elemental lithium in lithium carbonate and nickel cobalt manganese is 1.0-1.05: 1.
2. nickel-cobalt-manganese ternary combination electrode material according to claim 1, it is characterised in that the nickel-cobalt-manganese ternary is compound
Electrode material is α-NaFeO2Layer structure.
3. nickel-cobalt-manganese ternary combination electrode material according to claim 1, it is characterised in that the modified carbon nano-tube is
Nitrogen modified carbon nano-tube；The nitrogen source of the nitrogen modified carbon nano-tube is melamine；Nitrogen and carbon in the melamine
The mass ratio of nanotube is：0.04-0.06∶0.94-0.96.
4. nickel-cobalt-manganese ternary combination electrode material according to claim 1, it is characterised in that the modified carbon nano-tube is
Boron modification CNT；The boron source of the boron modification CNT is boric acid；Boron element and CNT in the boric acid
Mass ratio is：0.04-0.06∶0.94-0.96.
5. nickel-cobalt-manganese ternary combination electrode material according to claim 1, it is characterised in that the modified carbon nano-tube is
Nitrogen modified carbon nano-tube and boron modification CNT；The nitrogen source of the nitrogen modified carbon nano-tube is melamine；The boron modification
The boron source of CNT is boric acid；The mass ratio of boron element in nitrogen, boric acid and CNT in the melamine
For：0.02-0.03∶0.02-0.03∶0.94-0.96.
6. a kind of preparation method of nickel-cobalt-manganese ternary combination electrode material as described in any one of claim 1 ~ 5, its feature exist
In it comprises the following steps：
（1）CNT, melamine and/or boric acid are mixed in mass ratio, is placed in nitrogen atmosphere and is calcined after ball milling, is calcined
Temperature is 400 DEG C -600 DEG C, and roasting time is 4-8 h, obtains modified carbon nano-tube；
（2）Lithium carbonate, nickel cobalt manganese are mixed in proportion, is added in absolute ethyl alcohol and is disperseed；
（3）By modified carbon nano-tube in positive electrode proportion, weigh modified carbon nano-tube and be placed in step（2）Described in
In ethanol, fully dispersed, ball milling, suspension is obtained；
（4）By step（3）Middle suspension is put in evaporating water in baking oven, obtains and dries presoma；
（5）By step（4）In drying presoma be placed in nitrogen atmosphere batch-type furnace and be sintered, sintering temperature is 700 DEG C-
900 DEG C, sintering time 12-24h, obtain the nickel-cobalt-manganese ternary combination electrode material of modified carbon nano-tube modification.
7. preparation method according to claim 5, it is characterised in that the step（2）The concentration of middle ethanol is 99.5%.
8. preparation method according to claim 5, it is characterised in that the step（3）Middle Ball-milling Time is 4-6 hours.
9. preparation method according to claim 5, it is characterised in that step（4）In drying condition be temperature 60-80
DEG C, the time is 8-14 hours.
10. preparation method according to claim 5, it is characterised in that the step（2）Elemental lithium in middle lithium carbonate with
The mol ratio of nickel cobalt manganese is more than 1.
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| CN110854384A (en) * | 2019-11-26 | 2020-02-28 | 河北省科学院能源研究所 | Preparation method of surface-modified nickel-based electrode material |
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| CN115353094A (en) * | 2022-07-18 | 2022-11-18 | 北京市科学技术研究院资源环境研究所 | Solid phase purification method of carbon nano tube |
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Cited By (5)
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| CN110854384A (en) * | 2019-11-26 | 2020-02-28 | 河北省科学院能源研究所 | Preparation method of surface-modified nickel-based electrode material |
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| CN115353094A (en) * | 2022-07-18 | 2022-11-18 | 北京市科学技术研究院资源环境研究所 | Solid phase purification method of carbon nano tube |
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