CN108390035A - The preparation method of graphene/trielement composite material - Google Patents
The preparation method of graphene/trielement composite material Download PDFInfo
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- CN108390035A CN108390035A CN201810132006.2A CN201810132006A CN108390035A CN 108390035 A CN108390035 A CN 108390035A CN 201810132006 A CN201810132006 A CN 201810132006A CN 108390035 A CN108390035 A CN 108390035A
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The invention belongs to field of lithium ion battery material preparation, specifically a kind of graphene/trielement composite material and preparation method thereof.It, which was prepared, is known as：Nickel ion, cobalt ions and its manganese ion are prepared first, is added in graphene oxide solution later, and hydrogel is prepared by hydro-thermal reaction, passes through low temperature drying, electrochemical deposition later, and graphene/trielement composite material is prepared in thermal reduction, sintering.Its graphene trielement composite material prepared can make metal ion Uniform Doped between graphene layer and its around using hydro-thermal method, and prepare high density ternary precursor, later lithium salts is deposited in its surface electrochemistry, prepare the persursor material high with consistency, consistency is high, and graphene is fully doped between ternary material by heat-treating, to significantly improve gram volume performance, conductivity and its imbibition liquid-keeping property of ternary material, to improve the high rate performance and cycle performance of battery.
Description
Technical field
The invention belongs to field of lithium ion battery material preparation, specifically a kind of graphene/trielement composite material
Preparation method.
Background technology
The raising that electric vehicle course continuation mileage is required with market, it is desirable that lithium ion battery has higher energy close
Degree, cryogenic property and its rapid charging performance.And the lithium ion battery of existing market is high with ternary battery energy density, the cycle longevity
It orders the advantages that long and is widely used in the fields such as electric vehicle, electric bus, but its energy density is relatively low, high rate performance is inclined
It is low, limit its popularization in some fields.Therefore the gram volume of ternary used in battery tertiary cathode material and its forthright again is improved
The hot spot studied at present can be become.And doping techniques are then presently the most one of common, best results methods, i.e., by material
Doping metals, oxide and its other materials improve the performance of its gram volume between material.
Such as patent（CN 1041578455 A）It discloses a kind of graphene oxide organic solvent and prepares graphene compound three
The method of first material, by improving the electric conductivity of ternary material, high rate performance, but stone in ternary material surface coated graphite alkene
Black alkene is poor to the uniform doping of material, and consistency degree is low, causes its volume energy density relatively low.
And hydro-thermal method is one of the method for preparing high-density graphite alkene, the material prepared is that have by formation of chemical bond
Have the advantages that consistency height, high uniformity, consistency are strong, and depositing lithium salts can be by lithium ion Uniform Doped into before ternary material
It drives between body and its graphene, has many advantages, such as that gram volume is high, conductivity is strong and its imbibition ability is strong, and lithium can be obviously improved
The chemical property of ternary material used in ion battery.
Invention content
The present invention provides a kind of preparation method of graphene/trielement composite material, improves current ternary material in conductivity
With the defect of the not high aspect of cycle performance deviation and its tap density, the present invention is prepared by hydro-thermal-electrochemistry combination method, tool
There are tap density height, conductivity strong and its characteristics such as cycle performance is excellent.
To achieve the above object, the technical solution adopted by the present invention is：
The composite material is that the graphene for being using ternary material as matrix and inside 1~10%wt doped with content forms, and is made
It is for process：
1）, metal ion preparation：
It is respectively cathode using pure metallic nickel, cobalt, manganese as anode, platinum electrode, the acetic acid of 0.1mol/L is electrolysis using two-probe method
Liquid is electrolysed under the conditions of the constant voltage of 2V, respectively obtains nickel ion, cobalt ions, manganese ion, later according to certain volume
It is mixed to get a concentration of（0.01~0.1）The metal ion mixed liquor A of mol/l；
Wherein：Molar ratio, nickel ion：Cobalt ions：Manganese ion=（0.7~0.9）：（0.05~0.15）：（0.05~0.15）
2）, hydrogel prepare：
100ml is weighed, it is a concentration of（1~10）The graphene oxide solution of mg/ml, is added later（0.01~0.1）The nitrogen source of g is stirred
After mixing uniformly, then add（100~1000）The mixed liquor A of ml after ultrasonic disperse is uniform, obtains solution B, is transferred to high pressure later
In reaction kettle, and in temperature it is（150~200）DEG C reaction（2~12）H obtains hydrogel, is in temperature later（30~80）℃
Vacuum drying（24~96）H obtains the high density graphene oxide composite material B doped with metal ion；
3）, ternary material precursor prepare：
Lithium salts is added to the solvent that 0.1mol/L is configured in methyl ethyl carbonate, later with high density graphene oxide composite wood
B is expected as working electrode, and platinum electrode is used as to electrode, and saturation calomel uses electrochemical deposition method in height as reference electrode
Density graphene oxide composite material B surface deposits lithium salts, finally obtains containing highdensity ternary material precursor C；
4）, sintering
It will be placed into tube furnace containing highdensity ternary material precursor C, and in argon gas hydrogen mixed gas（1:1）Atmosphere
Under, it is warming up to the heating rate of 5 DEG C/min（300~400）DEG C, and keep the temperature（1~3）H, later again with the heating of 5 DEG C/min
Rate is warming up to（800~900）DEG C, and keep the temperature（2~12）H cools to room temperature, and crushes under an argon atmosphere later, classification
Obtain graphene trielement composite material.
The step 2）In nitrogen source be pyrroles, aniline, melamine, urea, one kind in ammonium hydroxide；
The step 3）Lithium salts is difluorine oxalic acid boracic acid lithium；
The step 3）Electrochemical deposition method is one kind in cyclic voltammetry, constant-voltage method, constant flow method, impulse method.
Beneficial effects of the present invention：
1）Graphene hydrogel containing metal ion is prepared using hydro-thermal method, metal ion can be with Uniform Doped into graphene
Between, and the high graphene ternary material precursor of consistency is formed after low temperature drying, thermal reduction, play its graphene conductive
Rate is high, specific surface is big and its characteristics such as mechanical strength is high, and the gram volume for finally improving its ternary material plays and its conductivity.
2）Lithium salts is deposited on ternary material precursor surface by electrochemical deposition method, mixes, has uniform compared with solid phase method
Degree is high, the contact area ambassador between material reacts abundant after it in sintering process, improves the electrochemistry such as the specific capacity of material
Performance.
Description of the drawings
Fig. 1 is the SEM figures for graphene/trielement composite material that embodiment 1 is prepared.
Specific implementation mode
Embodiment 1
1）, metal ion preparation：
It is respectively cathode using pure metallic nickel, cobalt, manganese as anode, platinum electrode, the acetic acid of 0.1mol/L is electrolysis using two-probe method
Liquid is electrolysed under the conditions of the constant voltage of 2V, respectively obtains the nickel ion, cobalt ions, manganese ion of a concentration of 0.1mol/L, it
Afterwards according to 8：1：1 volume mixture obtains the metal ion mixed liquor A of a concentration of 0.05mol/L；
2）, hydrogel prepare：
100ml is weighed, the graphene oxide solution of a concentration of 5mg/ml after the pyrroles of addition 0.05g stirs evenly later, then adds
The mixed liquor A for adding 500ml after ultrasonic disperse is uniform, obtains solution B, is transferred in autoclave later, and is in temperature
180 DEG C of reaction 6h, obtain hydrogel, are later 50 DEG C of dry 48h in temperature, obtain the high density oxidation doped with metal ion
Graphene composite material B；
3）, ternary material precursor prepare：
Difluorine oxalic acid boracic acid lithium is added to the solvent for being configured to 0.1mol/L in methyl ethyl carbonate, stone is aoxidized with high density later
Black alkene composite material B is as working electrode, and platinum electrode is used as to electrode, and saturation calomel is as reference electrode, above-mentioned solvent conduct
Electrolyte, and use cyclic voltammetry（- 2V-2V, surface sweeping speed .5mv/S）In its high density graphene oxide composite material B table
Face deposits lithium salts 10min, finally obtains containing highdensity ternary material precursor C；
4）, sintering
It will be placed into tube furnace containing highdensity ternary material precursor C, and in argon gas hydrogen 1:Under the atmosphere of 1 mixing,
350 DEG C are warming up to the heating rate of 5 DEG C/min, and keeps the temperature 2h, is warming up to 850 DEG C again with the heating rate of 5 DEG C/min later,
And 6h is kept the temperature, cool to room temperature under an argon atmosphere later, and crush, classification obtains graphene trielement composite material.
SEM is tested：Fig. 1 is the SEM pictures for graphene/trielement composite material that embodiment 1 is prepared, by that can be seen in figure
Go out, material presentation is spherical, is made of second particle, grain size is（1~10）μm.
Embodiment 2
1）, metal ion preparation：
It is respectively cathode using pure metallic nickel, cobalt, manganese as anode, platinum electrode, the acetic acid of 0.1mol/L is electrolysis using two-probe method
Liquid is electrolysed under the conditions of the constant voltage of 2V, respectively obtains nickel ion, cobalt ions, manganese ion, later according to certain volume
Than 9：0.5：0.5 is mixed to get the metal ion mixed liquor A of a concentration of 0.1mol/l；
2）, hydrogel prepare：
Weigh 100ml, the graphene oxide solution of a concentration of 1mg/ml, add later 0.01g melamine stir evenly after,
The mixed liquor A for adding 100ml again after ultrasonic disperse is uniform, obtains solution B, is transferred in autoclave later, and in temperature
For 150 DEG C of reaction 2h, hydrogel is obtained, is later 30 DEG C of dry 96h in temperature, obtains the high density oxygen doped with metal ion
Graphite alkene composite material B；
3）, ternary material precursor prepare：
Difluorine oxalic acid boracic acid lithium is added to the solvent for being configured to 0.1mol/L in methyl ethyl carbonate, stone is aoxidized with high density later
Black alkene composite material B is as working electrode, and platinum electrode is used as to electrode, and saturation calomel is as reference electrode, above-mentioned solvent conduct
Electrolyte, and use constant-voltage method（1.8V）20min is deposited in high density graphene oxide composite material B surface, finally obtains and contains
There is highdensity ternary material precursor C；
4）, sintering
It will be placed into tube furnace containing highdensity ternary material precursor C, and in argon gas hydrogen mixed gas（1:1）Atmosphere
Under, 300 DEG C are warming up to the heating rate of 5 DEG C/min, and keep the temperature 3h, are warming up to 900 again with the heating rate of 5 DEG C/min later
DEG C, and 2h is kept the temperature, cool to room temperature under an argon atmosphere later, and crush, classification obtains graphene trielement composite material.
Embodiment 3
1）, metal ion preparation：
It is respectively cathode using pure metallic nickel, cobalt, manganese as anode, platinum electrode, the acetic acid of 0.1mol/L is electrolysis using two-probe method
Liquid is electrolysed under the conditions of the constant voltage of 2V, respectively obtains nickel ion, cobalt ions, manganese ion, later according to certain volume
Than 7：1.5：1.5 are mixed to get the metal ion mixed liquor A of a concentration of 0.1mol/l；
2）, hydrogel prepare：
100ml is weighed, the graphene oxide solution of a concentration of 10mg/ml after the ammonium hydroxide aniline of addition 0.1g is uniform later, then adds
The mixed liquor A for adding 1000ml after ultrasonic disperse is uniform, obtains solution B, is transferred in autoclave later, and is in temperature
200 DEG C of reaction 2h, obtain hydrogel, and being 80 DEG C in temperature later dries the high density oxidation obtained for 24 hours doped with metal ion
Graphene composite material B；
3）, ternary material precursor prepare：
Difluorine oxalic acid boracic acid lithium is added to the solvent for being configured to 0.1mol/L in methyl ethyl carbonate, stone is aoxidized with high density later
Black alkene composite material B is as working electrode, and platinum electrode is used as to electrode, and saturation calomel is as reference electrode, above-mentioned solvent conduct
Electrolyte, and use constant flow method（10mA/cm2）60min is deposited in high density graphene oxide composite material B surface, finally
To containing highdensity ternary material precursor C；
4）, sintering
It will be placed into tube furnace containing highdensity ternary material precursor C, and in argon gas hydrogen mixed gas（1:1）Atmosphere
Under, 400 DEG C are warming up to the heating rate of 5 DEG C/min, and keep the temperature 1h, are warming up to 800 again with the heating rate of 5 DEG C/min later
DEG C, and 12h is kept the temperature, cool to room temperature under an argon atmosphere later, and crush, classification obtains graphene trielement composite material.
Comparative example：
Weigh 100g LiNi0.8Co0.1Mn0.1O2Ternary material precursor and the graphene solution of 50g a concentration of 5% add 500ml
Ethyl alcohol in, disperse 2h in the case where power is the ultrasound condition of 250W, after filtering, 100 DEG C of dryings, obtain trielement composite material forerunner
Body；It is transferred in tube furnace later, under the conditions of hydrogen atmosphere, is warming up to 800 DEG C with 5 DEG C/min, is sintered 6h, obtains graphene
Trielement composite material.
Button cell makes：
Button cell is dressed up as follows to the trielement composite material that embodiment 1-3 and comparative example are prepared and is tested：
1）It is added in 220mLN- methyl pyrrolidones in 95g positive electrodes, 1g Kynoar, 4g conductive agents SP, stirring is equal
It is even to prepare anode sizing agent, it is coated on copper foil, drying, roll pressing obtains anode pole piece.
Electrolyte uses lithium hexafluoro phosphate（LiPF6）For electrolyte, a concentration of 1.3mol/L, volume ratio 1:1 carbonic acid
Vinyl acetate（EC）And diethyl carbonate（DEC）For solvent, metal lithium sheet is used as to electrode, and diaphragm uses polyethylene (PE), and poly- third
Alkene (PP) or poly- second propylene (PEP) composite membrane, in the glove box for being flushed with hydrogen gas according to existing method assemble button cell A1, A2 and
B1。
2）Above-mentioned button cell is tested on new prestige 5V/10mA type cell testers, charging/discharging voltage range 3-4.3V,
Charge-discharge magnification 0.1C, test result are as shown in table 1.
1 button cell test result of table
As can be seen from Table 1, embodiment prepares the gram volume of trielement composite material and its first charge discharge efficiency is better than comparative example, former
Gram volume because that by metal ion Uniform Doped between graphene, can improve material using water-gel method plays efficiency, together
Shi Caiyong electrochemical deposition lithium salts enables its lithium salts fully to contact the gram volume hair for improving material with nickel cobalt manganese metal ion
It waves.
3）Soft-package battery is tested
1）High rate performance
Using the material that Examples 1 to 2 and comparative example are prepared as positive electrode.Using artificial graphite as cathode, with LiPF6It is (molten
Agent is EC+DEC, volume ratio 1：1, concentration 1.3mol/L) it is electrolyte, celegard2400 is that diaphragm prepares 5Ah Soft Roll electricity
Pond C1, C2 and D.It charges later with 0.3C multiplying powers, blanking voltage 4.2V is discharged with 0.3C later, electric discharge cut-off
Voltage 3.0V, finally prepares soft-package battery.
The high rate performance of its ternary soft-package battery, charging/discharging voltage 3.0~4.2V of range, temperature 25 ± 3.0 are tested later
DEG C, it is charged with 0.5C, 1.0C, 5.0C, 10.0C, 20.C, is discharged with 0.5C.
Table 2, embodiment are compared with the multiplying power of comparative example
As shown in Table 2, the multiplying power charging performance of soft-package battery is substantially better than comparative example in embodiment 1 ~ 3, i.e. the charging time is shorter,
Analysis reason is：By graphene strong electron transfer rate and its mechanical strength, the transmission speed of electronics under big multiplying power is improved
Rate, while the characteristic for having granularity small using lithium salts prepared by sedimentation, improve the lithium ion transport rate of material.
2）Cycle performance
It is later 1.0C with rate of charge, discharge-rate 1.0C, voltage range 3.0-4.3V test following for its soft-package battery
Ring performance（500 times）.
3 cycle performance of table compares
As can be seen from Table 3, the soft-package battery cycle performance that embodiment is prepared is better than comparative example, the reason for this is that being mixed in material
Miscellaneous nitrogen-atoms has the function of that material structure is promoted to stablize and its combine the characteristic of graphene high conductivity, can further carry
The cycle performance of its high material.
Claims (6)
1. a kind of preparation method of graphene/trielement composite material, which is characterized in that the composite material is using ternary material as base
Body is simultaneously formed in inside doped with the graphene that content is 1~10%wt, and preparation process is：
1）, metal ion solution preparation：
Nickel ion solution, cobalt ions solution, manganese ion solution are prepared, it is 0.01~0.1mol/L to be mixed to get concentration of metal ions
Mixed liquor A, wherein each metal ion molar ratio, nickel ion：Cobalt ions：Manganese ion=（0.7~0.9）：（0.05~0.15）：
（0.05~0.15）；
2）, hydrogel prepare：
The graphene oxide solution of a concentration of 1~10mg/ml is weighed, after addition nitrogen source stirs evenly later, then adds mixed liquor
A, then ultrasonic disperse is uniform, obtains solution B, is transferred in autoclave later, and is 150~200 DEG C of ranges in temperature
Between react 2~12h, obtain hydrogel, be then that 30~80 DEG C of ranges are dried in vacuo 24~96h in temperature by above-mentioned hydrogel,
Obtain the high density graphene oxide composite material B doped with metal ion；
3）, ternary material precursor prepare：
Lithium salts is added to the solvent for being configured to that lithium salt is 0.1mol/L in methyl ethyl carbonate, stone is aoxidized with high density later
Black alkene composite material B is as working electrode, and platinum electrode is used as to electrode, and saturation calomel is heavy using electrochemistry as reference electrode
High density graphene oxide composite material B is put into solvent by area method carries out surface deposition lithium salts, finally obtains containing high density
The ternary material precursor C of graphene oxide；
4）, sintering
Ternary material precursor C containing high density graphene oxide is calcined, is calcined in argon gas and hydrogen 1:1 mixing
It is carried out under atmosphere, is to be warming up to the heating rate of 5 DEG C/min（300~400）DEG C, and keep the temperature（1~3）H, later again with 5 DEG C/
Min heating rates are to be warming up to（800~900）DEG C, and keep the temperature（2~12）H cools to room temperature under an argon atmosphere later, and
It crushes, classification obtains graphene trielement composite material.
2. the preparation method of graphene/trielement composite material according to claim 1, which is characterized in that the step
1）Middle to prepare metal ion solution using two-probe method, respectively using pure metallic nickel, cobalt, manganese as anode, platinum electrode is cathode,
The acetic acid of 0.1mol/L is electrolyte, is electrolysed under the conditions of the constant voltage of 2V, obtains metal ion solution.
3. the preparation method of graphene/trielement composite material according to claim 1, which is characterized in that the step
2）In nitrogen source be pyrroles, aniline, melamine, urea, one kind in ammonium hydroxide.
4. the preparation method of graphene/trielement composite material according to claim 1, which is characterized in that the step
3）Lithium salts is difluorine oxalic acid boracic acid lithium.
5. the preparation method of graphene/trielement composite material according to claim 1, which is characterized in that the step
3）Electrochemical deposition method is one kind in cyclic voltammetry, constant-voltage method, constant flow method, impulse method.
6. the preparation method of graphene/trielement composite material according to claim 1, which is characterized in that step 2）Solution B
The graphene oxide solution for weighing a concentration of 1~10mg/ml of 100ml is prepared, the nitrogen source stirring for adding 0.01~0.1g later is equal
After even, then the mixed liquor A of 100~1000ml is added, then ultrasonic disperse is uniform, obtains solution B.
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Cited By (9)
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| CN109100408A (en) * | 2018-09-25 | 2018-12-28 | 山西大学 | It is a kind of based on iron-phthalocyanine/nitrogen, the electrochemical sensor of boron doping redox graphene and its preparation method and application |
| CN109841812A (en) * | 2019-01-25 | 2019-06-04 | 四川师范大学 | A kind of ternary cobalt acid nickel lithium ion battery negative material of sandwich structure and preparation method thereof |
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| CN110511402A (en) * | 2019-09-12 | 2019-11-29 | 东华大学 | A kind of cobalt cross-linked hydrogel and preparation method thereof with high cross-link intensity |
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| CN110931759B (en) * | 2019-12-19 | 2021-04-27 | 安徽正熹标王新能源有限公司 | Al (aluminum)2O3Coated Co-W double-doped LiNiO2Lithium ion battery anode material and preparation method thereof |
| CN113929152A (en) * | 2020-07-14 | 2022-01-14 | 恒大新能源技术(深圳)有限公司 | Composite material precursor, composite material, preparation method of composite material and positive plate |
| CN114275826A (en) * | 2021-12-14 | 2022-04-05 | 湖北容百锂电材料有限公司 | Graphene carbon surface modified nickel cobalt lithium manganate ternary positive electrode material and preparation method thereof |
| CN114275826B (en) * | 2021-12-14 | 2023-02-28 | 湖北容百锂电材料有限公司 | Graphene carbon surface modified nickel cobalt lithium manganate ternary positive electrode material and preparation method thereof |
| CN114759182A (en) * | 2022-05-25 | 2022-07-15 | 昆明理工大学 | Graphene-coated tin oxalate negative electrode material, preparation method thereof and battery |
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Application publication date: 20180810 |