CN108682799A - Carbon-coated anode material for lithium-ion batteries and preparation method thereof - Google Patents
Carbon-coated anode material for lithium-ion batteries and preparation method thereof Download PDFInfo
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- CN108682799A CN108682799A CN201810371081.4A CN201810371081A CN108682799A CN 108682799 A CN108682799 A CN 108682799A CN 201810371081 A CN201810371081 A CN 201810371081A CN 108682799 A CN108682799 A CN 108682799A
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- H—ELECTRICITY
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H01M4/00—Electrodes
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The present invention relates to lithium ion battery, a kind of carbon-coated anode material for lithium-ion batteries and preparation method thereof is disclosed, it is Ni that this method, which includes by chemical formula,0.6Co0.2Mn0.2(OH)2Nickelic presoma, Li source compound, inorganic oxidizer be ground stirring, preheat, heat up after preheating, keep the temperature, keep the temperature postcooling, obtain precursor material；It is added dropwise to hydrogen peroxide in the mixture of cyclodextrin and glacial acetic acid, it is lasting to mix, glycerine and Bi-phenolic Methan e are added, carbon source object is obtained；Ultrasonic mixing in carbon source object, heat drying is added in precursor material.The cell positive material has higher discharge capacity and good cycle performance, it need not for a long time be roasted in the case where carbon source coats in preparation process, effectively control the consistency of material, and this prepares raw material and is easy to get, preparation method is simple, has higher application value.
Description
Technical field
The present invention relates to lithium ion batteries, and in particular, to a kind of carbon-coated anode material for lithium-ion batteries and its system
Preparation Method.
Background technology
With the development of ev industry, power lithium-ion battery demand constantly increases.However, lithium ion power is electric
Requirement higher of the pond to the capacity of battery material, safety and cyclicity etc..Currently, LiFePO4 in the market and common
Ternary lithium ion battery battery material has been increasingly difficult to meet the requirement of power battery, and there is an urgent need for develop new lithium ion battery
Positive electrode.
For lithium ion battery, positive electrode is one of the key factor for improving its performance, has high safety, low cost
The positive ternary material of advantage is concerned, but is it the shortcomings that tertiary cathode material in high power charging-discharging,
Capacity attenuation is very fast, and high rate performance is bad.For its disadvantage, coated modified carbon research also has become the heat that researcher pursues
Point.
Carbon source (such as glucose, citric acid, sucrose) can surface of positive electrode active material formed carbon-coating, to improve its
Electric charge transfer rate in redox reaction and more stable.The chemical property of tertiary cathode material is carried after the packet carbon of surface
Height, this is because its electronic conductivity enhances after packet carbon, because carbon, which is distributed in tertiary cathode material particle surface, contributes to electricity
The transfer of son and the polarization for reducing battery.Positive electrode of the tertiary cathode material as lithium ion battery, is lithium ion battery
Important component is the highest part of cost in lithium ion battery, is the critical material for influencing performance of lithium ion battery.
Currently, the research for packet carbon modified technique is substantially unfolded around conventional method.South Korea Hyun-SooKim et al. is first
Polycarboxylate sodium and carbon black are put in distilled water and disperse simultaneously ball milling 2h, is coagulated after it is then stirred 2h at 50 DEG C
Glue；Gel is dissolved in distilled water later, while the LiNi of 50g is added1/3Mn1/3Co1/3O21h is stirred, then by the pH of solution
It is adjusted to 4~5；Finally, it is carried out filtering and roasts 3h at 300 DEG C, obtain final products LiNi1/3Mn1/3Co1/3O2/C。
Domestic aspect, Chinese Academy of Sciences BinLin et al. by keeping the temperature 10h after raw material is heated to 950 DEG C in air, are made porous first
Spherical LiNi1/3Mn1/3Co1/3O2Positive electrode；Its packet carbon technique is as follows：Citric acid is dissolved in (as carbon source) first anhydrous
In ethyl alcohol, LiNi is then allowed1/3Mn1/3Co1/3O2Particle is spread in the solution；Under vacuum conditions, it is two small to be stirred solution
When make citric acid fully penetrated to LiNi1/3Mn1/3Co1/3O2In pellet pores；After drying, solid chemical compound with 600 DEG C in sky
It is roasted in gas, 0.5h is to obtain the LiNi of surface packet carbon for heat preservation1/3Mn1/3Co1/3O2Material.Since carbon is common reducing agent,
Itself in roasting and LiNi1/3Mn1/3Co1/3O2Particle contacts, and may result in transition metal ions and is reduced to lower valency, to,
Make in sintering process, the LiNi optimized1/3Mn1/3Co1/3O2Performance be compromised.
Above two technique, since roasting time is longer, this adverse effect is difficult to control, and leads to the performance of resulting materials
Consistency is difficult to control.
Invention content
It uses and is deposited in carbon source it is an object of the invention to overcome in the prior art carbon-coated positive electrode in order to obtain
The technique roasted for a long time in case, and this is overcome due to roasting between time-out so that transition metal ions is gone back by part
Original so that material the uppity defect of consistency, the present invention provides a kind of carbon-coated anode material for lithium-ion batteries and
Preparation method, the cell positive material have higher discharge capacity and good cycle performance, are not required in preparation process
It to be roasted for a long time in the case where carbon source coats, effectively control the consistency of material, and this prepares raw material and is easy to get, preparation method
Simply, there is higher application value.
To achieve the goals above, the present invention provides a kind of preparation sides of carbon-coated anode material for lithium-ion batteries
Method, the preparation method comprises the following steps：(1) it is Ni by chemical formula0.6Co0.2Mn0.2(OH)2Nickelic presoma, lithium source
Conjunction object, inorganic oxidizer are ground stirring, preheat, heat up after preheating, keep the temperature, and keep the temperature postcooling, obtain precursor material；(2) in
It is added dropwise to hydrogen peroxide in the mixture of cyclodextrin and glacial acetic acid, it is lasting to mix, glycerine and Bi-phenolic Methan e are added, carbon source is obtained
Object；(3) ultrasonic mixing in carbon source object, heat drying is added in precursor material.
The present invention also provides a kind of carbon-coated lithium ion batteries being prepared according to previously described preparation method
Positive electrode.
Through the above technical solutions, the present invention provides a kind of carbon-coated anode material for lithium-ion batteries and its preparation sides
Method, the cell positive material have higher discharge capacity and good cycle performance, need not be in carbon source in preparation process
It is roasted for a long time in the case of cladding, effectively controls the consistency of material, and this prepares raw material and is easy to get, preparation method is simple, tool
There is higher application value.The present invention overcomes in the prior art carbon-coated positive electrode in order to obtain and uses in carbon source
In the presence of the technique that roasts for a long time, and overcome this due to roasting between time-out so that transition metal ions is by part
Reduction makes the uppity defect of consistency of material.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Specific implementation mode
The specific implementation mode of the present invention is described in detail below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of preparation method of carbon-coated anode material for lithium-ion batteries, the preparation method includes
Following steps：(1) it is Ni by chemical formula0.6Co0.2Mn0.2(OH)2Nickelic presoma, Li source compound, inorganic oxidizer carry out
Grinding stirring, preheating heat up after preheating, keep the temperature, and keep the temperature postcooling, obtain precursor material；(2) in the mixing of cyclodextrin and glacial acetic acid
Hydrogen peroxide is added dropwise in object, it is lasting to mix, glycerine and Bi-phenolic Methan e are added, carbon source object is obtained；(3) precursor material is added
Ultrasonic mixing in carbon source object, heat drying.
Through the above technical solutions, the present invention provides a kind of carbon-coated anode material for lithium-ion batteries and its preparation sides
Method, the cell positive material have higher discharge capacity and good cycle performance, need not be in carbon source in preparation process
It is roasted for a long time in the case of cladding, effectively controls the consistency of material, and this prepares raw material and is easy to get, preparation method is simple, tool
There is higher application value.The present invention overcomes in the prior art carbon-coated positive electrode in order to obtain and uses in carbon source
In the presence of the technique that roasts for a long time, and overcome this due to roasting between time-out so that transition metal ions is by part
Reduction makes the uppity defect of consistency of material.
In a kind of preferred embodiment of the present invention, there is higher discharge capacity and good cyclicity in order to obtain
Can carbon-coated anode material for lithium-ion batteries, it is preferable that Li and inorganic oxidizer in nickelic presoma, Li source compound
The ratio between amount of substance is 1:1.04-1.06:0.05-0.1.
In a kind of preferred embodiment of the present invention, there is higher discharge capacity and good cyclicity in order to obtain
The carbon-coated anode material for lithium-ion batteries of energy, it is preferable that in parts by weight, relative to 100 parts of cyclodextrin, the use of glycerine
Amount is 20-40 parts, and the dosage of Bi-phenolic Methan e is 20-40 parts, and the dosage of glacial acetic acid is 5-15 parts, and the dosage of hydrogen peroxide is
25-28 parts.
In a kind of preferred embodiment of the present invention, there is higher discharge capacity and good cyclicity in order to obtain
The carbon-coated anode material for lithium-ion batteries of energy, it is preferable that the rate of addition of hydrogen peroxide is 2-5mL/min.
In a kind of preferred embodiment of the present invention, there is higher discharge capacity and good cyclicity in order to obtain
The carbon-coated anode material for lithium-ion batteries of energy, it is preferable that the incorporation time in step (2) is to be added dropwise since hydrogen peroxide
It is added dropwise rear 20-30min to hydrogen peroxide, stir speed (S.S.) when mixing is 100-200r/min.
In a kind of preferred embodiment of the present invention, there is higher discharge capacity and good cyclicity in order to obtain
The carbon-coated anode material for lithium-ion batteries of energy, it is preferable that the mass ratio of precursor material and carbon source object is 1：0.5-0.8.
In a kind of preferred embodiment of the present invention, there is higher discharge capacity and good cyclicity in order to obtain
Can carbon-coated anode material for lithium-ion batteries, it is preferable that the condition of ultrasonic mixing includes：Frequency is 60-150kHZ, time
For 20-30min.
In a kind of preferred embodiment of the present invention, there is higher discharge capacity and good cyclicity in order to obtain
The carbon-coated anode material for lithium-ion batteries of energy, it is preferable that the temperature of heat drying is no more than 80 DEG C.
In a kind of preferred embodiment of the present invention, there is higher discharge capacity and good cyclicity in order to obtain
The carbon-coated anode material for lithium-ion batteries of energy, it is preferable that the time of grinding stirring is 10-20min in step (1).
In a kind of preferred embodiment of the present invention, there is higher discharge capacity and good cyclicity in order to obtain
Can carbon-coated anode material for lithium-ion batteries, it is preferable that preheating condition includes：Preheating temperature is 300~600 DEG C.
In a kind of preferred embodiment of the present invention, there is higher discharge capacity and good cyclicity in order to obtain
The carbon-coated anode material for lithium-ion batteries of energy, it is preferable that preheating time is 3~6 hours.
In a kind of preferred embodiment of the present invention, there is higher discharge capacity and good cyclicity in order to obtain
The carbon-coated anode material for lithium-ion batteries of energy, it is preferable that atmospheric condition is air atmosphere.
In a kind of preferred embodiment of the present invention, there is higher discharge capacity and good cyclicity in order to obtain
Can carbon-coated anode material for lithium-ion batteries, it is preferable that heat-retaining condition includes：Temperature is 700~950 DEG C.
In a kind of preferred embodiment of the present invention, there is higher discharge capacity and good cyclicity in order to obtain
The carbon-coated anode material for lithium-ion batteries of energy, it is preferable that soaking time is 15~20 hours.
In a kind of preferred embodiment of the present invention, there is higher discharge capacity and good cyclicity in order to obtain
The carbon-coated anode material for lithium-ion batteries of energy, it is preferable that heat preservation atmosphere is oxygen atmosphere.
In a kind of preferred embodiment of the present invention, there is higher discharge capacity and good cyclicity in order to obtain
The carbon-coated anode material for lithium-ion batteries of energy, it is further preferred that the concentration of oxygen is not less than 85%.
In a kind of preferred embodiment of the present invention, there is higher discharge capacity and good cyclicity in order to obtain
The carbon-coated anode material for lithium-ion batteries of energy, it is preferable that heating rate is 8~10 DEG C/min after preheating.
In a kind of preferred embodiment of the present invention, there is higher discharge capacity and good cyclicity in order to obtain
The carbon-coated anode material for lithium-ion batteries of energy, it is preferable that the rate of temperature fall for keeping the temperature postcooling is 8~10 DEG C/min.
For Li source compound, those skilled in the art can select in wider range, traditional lithium-ion battery system
Standby lithium source can meet the requirement of the present invention.In a kind of preferred embodiment of the present invention, there is higher put in order to obtain
The carbon-coated anode material for lithium-ion batteries of capacitance and good cycle performance, it is preferable that Li source compound be lithium carbonate,
It is one or more in lithium acetate, lithium oxalate, lithium phosphate, lithium nitrate and lithium chloride.
In a kind of preferred embodiment of the present invention, there is higher discharge capacity and good cyclicity in order to obtain
The carbon-coated anode material for lithium-ion batteries of energy, it is preferable that described inorganic oxidizer is ammonium persulfate, potassium bichromate and high chlorine
It is one or more in sour potassium.
The present invention also provides a kind of carbon-coated lithium ion batteries being prepared according to previously described preparation method
Positive electrode.
Through the above technical solutions, the present invention provides a kind of carbon-coated anode material for lithium-ion batteries and its preparation sides
Method, which has higher discharge capacity and good cycle performance, and overcomes this due to being roasted between time-out
It burns so that transition metal ions is partially reduced the uppity defect of consistency so that material.
The present invention will be described in detail by way of examples below.
Embodiment 1
The preparation method of carbon-coated anode material for lithium-ion batteries, the preparation method comprises the following steps：
(1) it is Ni by chemical formula0.6Co0.2Mn0.2(OH)2Nickelic presoma, lithium carbonate, potassium bichromate be ground and stir
Mix 10min, wherein the ratio between amount of substance of Li and inorganic oxidizer is 1 in nickelic presoma, Li source compound:1.04:
0.05, in air atmosphere 300 DEG C preheat 6 hours, after preheating with 8 DEG C/min heat up, oxygen atmosphere (oxygen it is a concentration of
85%) 20 hours are kept the temperature in 700 DEG C in, with 8 DEG C/min of coolings after heat preservation, obtains precursor material；
(2) by cyclodextrin, glacial acetic acid is added, hydrogen peroxide, the dropwise addition of hydrogen peroxide are added dropwise in these mixtures
Speed is 2mL/min, lasting to mix, and incorporation time is to be added dropwise to hydrogen peroxide since hydrogen peroxide rear 30min is added dropwise,
Stir speed (S.S.) when mixing is 100r/min, adds glycerine and Bi-phenolic Methan e, obtains carbon source object；
Wherein, in parts by weight, relative to 100 parts of cyclodextrin, the dosage of glycerine is 20 parts, the dosage of Bi-phenolic Methan e
It it is 20 parts, the dosage of glacial acetic acid is 5 parts, and the dosage of hydrogen peroxide is 25 parts；
(3) precursor material is added in carbon source object with the frequency ultrasound mixing 30min of 60kHZ, wherein precursor material and carbon
The mass ratio of source object is 1：0.5, heat drying, the wherein temperature of heat drying are 60 DEG C.
Embodiment 2
The preparation method of carbon-coated anode material for lithium-ion batteries, the preparation method comprises the following steps：
(1) it is Ni by chemical formula0.6Co0.2Mn0.2(OH)2Nickelic presoma, lithium carbonate, potassium bichromate be ground and stir
Mix 20min, wherein the ratio between amount of substance of Li and inorganic oxidizer is 1 in nickelic presoma, Li source compound:1.06:0.1,
It preheats 3 hours for 600 DEG C, is heated up with 10 DEG C/min after preheating, in oxygen atmosphere (a concentration of 90%) of oxygen in air atmosphere
In in 950 DEG C keep the temperature 15 hours, with 10 DEG C/min of coolings after heat preservation, obtain precursor material；
(2) by cyclodextrin, glacial acetic acid is added, hydrogen peroxide, the dropwise addition of hydrogen peroxide are added dropwise in these mixtures
Speed is 5mL/min, lasting to mix, and incorporation time is to be added dropwise to hydrogen peroxide since hydrogen peroxide rear 20min is added dropwise,
Stir speed (S.S.) when mixing is 200r/min, adds glycerine and Bi-phenolic Methan e, obtains carbon source object；
Wherein, in parts by weight, relative to 100 parts of cyclodextrin, the dosage of glycerine is 40 parts, the dosage of Bi-phenolic Methan e
It it is 40 parts, the dosage of glacial acetic acid is 15 parts, and the dosage of hydrogen peroxide is 28 parts；
(3) by precursor material be added carbon source object in the frequency ultrasound mixing 20min of 150kHZ, wherein precursor material and
The mass ratio of carbon source object is 1：0.8, heat drying, the wherein temperature of heat drying are 80 DEG C.
Embodiment 3
The preparation method of carbon-coated anode material for lithium-ion batteries, the preparation method comprises the following steps：
(1) it is Ni by chemical formula0.6Co0.2Mn0.2(OH)2Nickelic presoma, lithium carbonate, potassium bichromate be ground and stir
Mix 15min, wherein the ratio between amount of substance of Li and inorganic oxidizer is 1 in nickelic presoma, Li source compound:1.05:
0.07, in air atmosphere 450 DEG C preheat 4.5 hours, after preheating with 9 DEG C/min heat up, oxygen atmosphere (oxygen it is a concentration of
90%) 18 hours are kept the temperature in 780 DEG C in, with 9 DEG C/min of coolings after heat preservation, obtains precursor material；
(2) by cyclodextrin, glacial acetic acid is added, hydrogen peroxide, the dropwise addition of hydrogen peroxide are added dropwise in these mixtures
Speed is 4mL/min, lasting to mix, and incorporation time is to be added dropwise to hydrogen peroxide since hydrogen peroxide rear 25min is added dropwise,
Stir speed (S.S.) when mixing is 150r/min, adds glycerine and Bi-phenolic Methan e, obtains carbon source object；
Wherein, in parts by weight, relative to 100 parts of cyclodextrin, the dosage of glycerine is 30 parts, the dosage of Bi-phenolic Methan e
It it is 30 parts, the dosage of glacial acetic acid is 10 parts, and the dosage of hydrogen peroxide is 27 parts；
(3) by precursor material be added carbon source object in the frequency ultrasound mixing 25min of 100kHZ, wherein precursor material and
The mass ratio of carbon source object is 1：0.65, heat drying, the wherein temperature of heat drying are 70 DEG C.
Comparative example 1
It is Ni by chemical formula0.6Co0.2Mn0.2(OH)2Nickelic presoma and lithium carbonate powder, wherein in nickelic presoma
The molar ratio of Li is 1 in total amount and lithium carbonate containing Ni, Co and Mn:1.05, the two is ground into stirring 10min；Again at 450 DEG C,
5h is preheated, wherein atmospheric condition is air atmosphere；After preheating, with heating rate for 9 DEG C/min, 800 DEG C are warming up to, is protected
Temperature 18 hours, heat preservation atmosphere be oxygen atmosphere, a concentration of the 85% of oxygen, after heat preservation rate of temperature fall be 10 DEG C/min, be cooled to
It 600 DEG C, anneals 15 hours, annealing atmosphere is oxygen atmosphere, a concentration of the 85% of oxygen, after annealing, naturally cool to room
Warm (20 DEG C).
Comparative example 2
It is Ni by chemical formula0.6Co0.2Mn0.2(OH)2Nickelic presoma, lithium carbonate, potassium bichromate be ground stirring
20min, wherein the ratio between amount of substance of Li and inorganic oxidizer is 1 in nickelic presoma, Li source compound:1.05:0.1, in
It preheats 3 hours for 600 DEG C in air atmosphere, is heated up with 8 DEG C/min after preheating, in oxygen atmosphere (concentration of oxygen is not less than 85%)
In in 900 DEG C keep the temperature 20 hours, with 8 DEG C/min of coolings after heat preservation.
Comparative example 3
(1) it is Ni by chemical formula0.6Co0.2Mn0.2(OH)2Nickelic presoma and lithium carbonate powder, wherein nickelic forerunner
The molar ratio of Li is in total amount and lithium carbonate in body containing Ni, Co and Mn：1:1.05, the two is ground into stirring 10min；Exist again
450 DEG C, 5h is preheated, wherein atmospheric condition is air atmosphere；After preheating, with heating rate for 9 DEG C/min, it is warming up to
800 DEG C, keep the temperature 18 hours, heat preservation atmosphere be oxygen atmosphere, a concentration of the 85% of oxygen, after heat preservation rate of temperature fall be 10 DEG C/minute
Clock, is cooled to 600 DEG C, anneals 15 hours, and annealing atmosphere is oxygen atmosphere, and a concentration of the 85% of oxygen, it is natural after annealing
(20 DEG C) are cooled to room temperature, precursor material is obtained；
(2) by cyclodextrin, glacial acetic acid is added, hydrogen peroxide, the dropwise addition of hydrogen peroxide are added dropwise in these mixtures
Speed is 4mL/min, lasting to mix, and incorporation time is to be added dropwise to hydrogen peroxide since hydrogen peroxide rear 25min is added dropwise,
Stir speed (S.S.) when mixing is 150r/min, adds glycerine and Bi-phenolic Methan e, obtains carbon source object；
Wherein, in parts by weight, relative to 100 parts of cyclodextrin, the dosage of glycerine is 30 parts, the dosage of Bi-phenolic Methan e
It it is 30 parts, the dosage of glacial acetic acid is 10 parts, and the dosage of hydrogen peroxide is 27 parts；
(3) by precursor material be added carbon source object in the frequency ultrasound mixing 30min of 150kHZ, wherein precursor material and
The mass ratio of carbon source object is 1：0.8, heat drying, the wherein temperature of heat drying are no more than 80 DEG C.
Detect example 1
By the positive electrode being prepared in the present embodiment 1-3 and comparative example 1-3 and acetylene black, Kynoar (PVDF)
It is 8 according to mass ratio:1:1 ratio uniform mixing, is then pressed into piece, then be made directly with the mode of punching using tablet press machine
Diameter is the thin slice of 6mm, and obtained thin slice is dried in vacuo 12 hours under the conditions of 100 DEG C, and electrode slice is made；With 1mol/L's
LIPF6 is electrolyte, and microporous polypropylene membrane (Celgard2400) is diaphragm, and metal lithium sheet is reference electrode, full of hydrogen
CR2032 type button cells are made in material in glove box.Under the conditions of 25 DEG C, the Land- of Wuhan Lan electricity companies is utilized
CT2001A battery test system button type batteries carry out constant current charge-discharge test, test voltage ranging from 2.7V~4.3V.
It finds after testing, button cell made from the positive electrode in Application Example 1-3 is first under the conditions of 1C charge and discharge
For secondary specific discharge capacity after 188-195mAh/g or so, 100 cycles, capacity remains at 180mAh/g or more, cycle performance
It is good.
And button cell made from the positive electrode in comparative example 1, under the conditions of 1C charge and discharge, first discharge specific capacity exists
172mAh/g or so, after 100 times recycle, capacity is maintained at 151mAh/g or so.
And button cell made from the positive electrode in comparative example 2, under the conditions of 1C charge and discharge, first discharge specific capacity exists
153mAh/g or so, after 100 times recycle, capacity is maintained at 131mAh/g or so.
And button cell made from the positive electrode in comparative example 3, under the conditions of 1C charge and discharge, first discharge specific capacity exists
175mAh/g or so, after 100 times recycle, capacity is maintained at 146mAh/g or so.
By testing result above it is found that discharge cycles stability of the positive electrode under high magnification of the present invention is apparent
To improvement.Therefore, the discharge cycles stability using the carbon coating post-processing positive electrode in the present invention under high magnification,
To make material property be improved.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail can carry out a variety of simple variants to technical scheme of the present invention within the scope of the technical concept of the present invention, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of preparation method of carbon-coated anode material for lithium-ion batteries, which is characterized in that the preparation method include with
Lower step：
(1) it is Ni by chemical formula0.6Co0.2Mn0.2(OH)2Nickelic presoma, Li source compound, inorganic oxidizer be ground and stir
It mixes, preheats, heat up after preheating, keep the temperature, keep the temperature postcooling, obtain precursor material；
(2) it is added dropwise to hydrogen peroxide in the mixture of cyclodextrin and glacial acetic acid, it is lasting to mix, add glycerine and diphenylol first
Alkane obtains carbon source object；
(3) ultrasonic mixing in carbon source object, heat drying is added in precursor material.
2. preparation method according to claim 1, wherein Li and inorganic oxidizer in nickelic presoma, Li source compound
The ratio between the amount of substance be 1:1.04-1.06:0.05-0.1.
3. preparation method according to claim 1, wherein in parts by weight, relative to 100 parts of cyclodextrin, glycerine
Dosage is 20-40 parts, and the dosage of Bi-phenolic Methan e is 20-40 parts, and the dosage of glacial acetic acid is 5-15 parts, and the dosage of hydrogen peroxide is
25-28 parts；
Preferably, the rate of addition of hydrogen peroxide is 2-5mL/min；
Preferably, the incorporation time in step (2) is to be added dropwise to hydrogen peroxide since hydrogen peroxide rear 20- is added dropwise
30min, stir speed (S.S.) when mixing are 100-200r/min.
4. preparation method according to claim 1, wherein the mass ratio of precursor material and carbon source object is 1：0.5-0.8；
Preferably, the condition of ultrasonic mixing includes：Frequency is 60-150kHZ, time 20-30min；
Preferably, the temperature of heat drying is no more than 80 DEG C.
5. according to claim 1-4 any one of them preparation methods, wherein the time of grinding stirring is 10- in step (1)
20min。
6. according to claim 1-4 any one of them preparation methods, wherein preheating condition includes：Preheating temperature be 300~
600℃；And/or preheating time is 3~6 hours；And/or atmospheric condition is air atmosphere.
7. according to claim 1-4 any one of them preparation methods, wherein heat-retaining condition includes：Temperature is 700~950 DEG C；
And/or soaking time is 15~20 hours；And/or heat preservation atmosphere is oxygen atmosphere, it is preferable that the concentration of oxygen is not less than
85%.
8. according to claim 1-4 any one of them preparation methods, wherein heating rate is 8~10 DEG C/min after preheating；
And/or it is 8~10 DEG C/min to keep the temperature the rate of temperature fall of postcooling.
9. according to claim 1-4 any one of them preparation methods, wherein Li source compound is lithium carbonate, lithium acetate, oxalic acid
It is one or more in lithium, lithium phosphate, lithium nitrate and lithium chloride；
And/or described inorganic oxidizer is one or more in ammonium persulfate, potassium bichromate and potassium hyperchlorate.
10. a kind of carbon-coated lithium ion battery being prepared according to claim 1-9 any one of them preparation methods is just
Pole material.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110112406A (en) * | 2019-06-12 | 2019-08-09 | 广州德塔吉能源科技有限公司 | Preparation method, cathode compositions and the lithium ion battery of cathode compositions |
| CN114373916A (en) * | 2022-01-17 | 2022-04-19 | 中国科学院化学研究所 | Preparation method of lithium battery particle surface passivation positive electrode material |
-
2018
- 2018-04-24 CN CN201810371081.4A patent/CN108682799A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110112406A (en) * | 2019-06-12 | 2019-08-09 | 广州德塔吉能源科技有限公司 | Preparation method, cathode compositions and the lithium ion battery of cathode compositions |
| CN110112406B (en) * | 2019-06-12 | 2020-09-22 | 广州德塔吉能源科技有限公司 | Preparation method of cathode composition, cathode composition and lithium ion battery |
| CN114373916A (en) * | 2022-01-17 | 2022-04-19 | 中国科学院化学研究所 | Preparation method of lithium battery particle surface passivation positive electrode material |
| CN114373916B (en) * | 2022-01-17 | 2023-09-19 | 中国科学院化学研究所 | Preparation method of lithium battery particle surface passivation cathode material |
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