CN109088062A - A kind of preparation method of the modified nickel ion doped material of polyimides cladding, Dopants - Google Patents
A kind of preparation method of the modified nickel ion doped material of polyimides cladding, Dopants Download PDFInfo
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Abstract
The present invention relates to the preparation methods of the modified nickel ion doped material of a kind of polyimides cladding, Dopants, it includes the following steps: that (1) weighs lithium carbonate, manganese dioxide, nickel oxide and the ammonium halide of stoichiometric ratio, ethyl alcohol or water is added, ground and mixed, obtained mixture is put and is dried in an oven, then sintering obtains the nickel lithium manganate cathode material of Dopants；(2) certain density polyamic acid solution is prepared, the nickel lithium manganate cathode material that step (1) obtains is added, stirs, filters, it is dry, hot imide reaction is carried out under protective atmosphere, obtains modified nickel lithium manganate cathode material；The Modified Nickel lithium manganate material that the present invention obtains, after being recycled 200 times under 1C multiplying power, capacity retention ratio is 90.8% under room temperature, and capacity retention ratio is 88.5% at 55 DEG C of high temperature, greatly improves the specific capacity and stable circulation performance under nickel lithium manganate cathode material room temperature and high temperature.
Description
Technical field
A kind of preparation method for the nickel ion doped material that the present invention relates to polyimides to coat, Dopants are modified,
Belong to lithium ion secondary battery anode material field.
Background technique
It currently, positive electrode serves not only as electrode material and directly participates in electrochemical reaction in lithium battery, and is reaction
The main provider of middle lithium ion, performance directly affect the every characteristic and index of battery, be lithium battery technology core and
It is crucial.One of research hotspot as positive electrode current material, high-voltage spinel type nickel ion doped (LiNi0.5Mn1.5O4) have
The advantages that discharge voltage is high, energy density is high, safety is excellent, relative inexpensiveness.The energy density of nickel ion doped reaches 650
Wh kg-1, it is significantly higher than energy density such as cobalt acid lithium (the 518 Wh kg of traditional material-1), LiMn2O4 (400 Wh kg-1), phosphorus
Sour iron lithium (495 Wh kg-1), and atmosphere protection is not needed in nickel lithium manganate cathode material preparation process, it can be directly in sky
It is sintered synthesis under gas atmosphere, so it is well suited for large-scale production, there is great researching value and application prospect.
Since nickel lithium manganate cathode material causes the material to exist in charge and discharge process with the high voltage platform of 4.7V
The problems such as high rate performance and poor cycle performance.Main cause is: one, in charge and discharge process nickel ion doped material structure quilt
It destroys, keeps lithium ion embedding from normally returning, cause capacity attenuation；Two, its high voltage makes electrolyte decomposition, and decomposition product can be with electricity
Pole material reacts, and increases internal resistance, hinders the deintercalation of lithium ion, and lithium source is lost, leads to capacity attenuation, make cycle life by
It influences, therefore nickel ion doped material is modified, the emphasis studied in the industry with overcoming its defect to become.
CN105355903A discloses a kind of anode material for lithium-ion batteries and preparation method thereof based on nickel ion doped,
Anode uses the alumina-coated object of nickel ion doped, for improving the energy density, fast charging and discharging ability and cyclicity of battery
Can, and available high magnification quick charge.
CN108023081A discloses a kind of preparation method of the nickel lithium manganate cathode material of Al doping vario-property, with nitric acid
Nickel, manganese nitrate and lithium nitrate are raw material, and three is added in citric acid solution, is sprayed after being ultrasonically treated through high frequency sprayer
Out, the cloudy solution of ejection is in 600 DEG C of rapid draings；Nickel ion doped LiNi is obtained after desciccate sintering0.5Mn1.5O4Positive material
Expect that nickel ion doped LiNi is made0.5Mn1.5O4Positive electrode；Then by alumina powder and gained nickel ion doped LiNi0.5Mn1.5O4
Positive electrode mixing, and dehydrated alcohol is added, after ultrasound, dries and be sintered, obtain the nickel ion doped of Al doping vario-property
LiNi0.5Mn1.5O4Positive electrode powder.The nickel ion doped LiNi of the Al doping vario-property0.5Mn1.5O4Positive electrode is at circulation 30 times
Specific capacity conservation rate is 91.2% afterwards, greatly improves nickel ion doped LiNi0.5Mn1.5O4The stable circulation performance of positive electrode.
CN106992294A discloses a kind of preparation method of high-voltage lithium nickel manganate anode composite material, by the preparation side
High-voltage lithium nickel manganate anode composite material obtained by method and application the high-voltage lithium nickel manganate anode composite material lithium from
Sub- battery, wherein the preparation method of the high-voltage lithium nickel manganate anode composite material is the following steps are included: by lithium salts, the source M
It closes object, nickel salt and manganese salt to be dissolved in deionized water, and is added drop-wise in ionic liquid, obtain solution；The solution is carried out old
Change processing, obtains the first product；Predecomposition processing and sintering processes are carried out to first product, obtain the second product, it is described
Second product is the nickel ion doped particle doped with M ion；Second product and carbon-source cpd are mixed, is produced in described second
The coated with carbon bed of object obtains the high-voltage lithium nickel manganate anode composite material.The nickel ion doped material that the program obtains
It has excellent performance.
CN103474649A discloses a kind of method of modifying of lithium ion battery nickel lithium manganate cathode material, and feature exists
In, comprising: nickel ion doped and surface modifier are added to the water and ultrasonic disperse 10-20min, oxidant ultrasound is then added
5-15min, then the epolamine solution that concentration is 0.1-0.5mol/L is added dropwise, continue ultrasound 5-15min after being added dropwise,
Static aging 1-3h is filtered, washing, the nickel lithium manganate cathode material of polypyrrole coating modification to obtain the final product after 80-100 DEG C of drying,
Middle polypyrrole covering amount is the 0.5-5% of material gross mass.The specific surface of the nickel lithium manganate cathode material of this method preparation reduces,
With excellent processing performance, and it is applied to lithium ion battery, cycle performance is more excellent.
CN104828868A discloses a kind of preparation method of anode material for lithium-ion batteries graphene coated nickel ion doped:
(1) nickel ion doped precursor is prepared；(2) graphene dimethyl formamide solution is configured；(3) graphene for obtaining step (2)
Dimethyl formamide solution is added drop-wise to ultrasound in the nickel ion doped precursor of step (1) acquisition, and volatilizing acquisition, to be mixed with graphene thin
The nickel ion doped presoma of piece；(4) the nickel ion doped precursor preparation for being mixed with graphene platelet that calcining step (3) obtains obtains
The nickel ion doped of anode material for lithium-ion batteries graphene coated, the obtained graphene coated nickel ion doped of this method, cladding
Rate is high, and purity is high, specific capacity is high, good cycling stability.
Covering material in the prior art is mainly the good simple substance or compound of stability, including metal simple-substance, metal oxygen
Compound, phosphate and other inorganic matters etc., spray metal simple substance can hinder the diffusion of lithium ion and reduce the surface-active of material.
Phosphatic cladding increases the resistance between material and electrolyte, hinders the insertion and removing of lithium ion, therefore find one
The method of modifying that nickel ion doped material property can be improved in kind is particularly important.
Summary of the invention
The present invention is to solve problems of the prior art, and it is an object of the present invention to provide a kind of polyimides cladding, halogen family member
The preparation method of the nickel ion doped material of plain doping vario-property.
To achieve the above object, the technical solution used in the present invention is:
The preparation method of the modified nickel ion doped material of a kind of polyimides cladding, Dopants comprising following steps:
(1) lithium carbonate, manganese dioxide, nickel oxide and the ammonium halide of stoichiometric ratio are weighed, ethyl alcohol or water is added, grinding is mixed
It closes, obtained mixture is put and is dried in an oven, then sintering obtains the nickel lithium manganate cathode material powder of Dopants
End；
(2) the equal phthalic acid and 4 of stoichiometric ratio is weighed, 4 '-diaminodiphenyl ethers are closed using dimethyl acetamide as solvent
The polyamic acid solution for being 10% at concentration then prepares certain density polyamic acid solution, and the nickel that step (1) obtains is added
Manganate cathode material for lithium powder stirs, and filters, dry, then carries out hot imide reaction in a nitrogen atmosphere, obtains polyamides
The modified nickel ion doped material of imines cladding, Dopants；
The ammonium halide is selected from ammonium fluoride, ammonium chloride or ammonium bromide.
Further, in the step (1) lithium carbonate, nickel oxide and manganese dioxide molar ratio Li:Ni:Mn=1.05:
0.5:1.5, the additional amount of ammonium halide are x moles (it is modified to obtain Dopants for x=0.01,0.02,0.03 or 0.04)
Nickel ion doped material LiNi0.5Mn1.5O4-xFX, LiNi0.5Mn1.5O4-xClX, LiNi0.5Mn1.5O4-xBrX。
Further, ground and mixed in the step (1), for mixing is sanded, sands milling revolving speed is 2000 turns/min, and the time is
1~3h。
Further, drying temperature is 105 ± 2 DEG C in the step (1).
Further, sintering temperature is 900 DEG C in the step (1), is sintered 7 ~ 10h.
Further, a certain concentration is 1% polyamic acid solution in the step (2).
Further, the additional amount of nickel lithium manganate cathode material powder is 5g in the step (2).
Further, the temperature of hot imide reaction is at 100 DEG C, 200 DEG C, 300 DEG C, 450 DEG C in the step (2)
1 ~ 2h of each processing.
Further, drying condition in the step (2) are as follows: 40 ± 5 DEG C of vacuum drying 4h.
Further, more have the scheme of choosing as follows:
The preparation method of the modified nickel ion doped material of above-mentioned polyimides cladding, Dopants comprising following steps:
(1) weigh the lithium carbonate, manganese dioxide and nickel oxide of molar ratio Li:Ni:Mn=1.05:0.5:1.5, be added x moles (x=
0.01,0.02,0.03 or NH 0.04)4Ethyl alcohol or water is added in F, and 1 ~ 3h of mixing is sanded, and sand milling revolving speed is 2000 turns/min,
Obtained mixture is put and is dried in an oven, 7 ~ 10h is sintered at 900 DEG C and obtains the nickel ion doped anode of Dopants
Material powder LiNi0.5Mn1.5O4-xAX, A is selected from F, Br or Cl；
(2) the equal phthalic acid and 4 that molar ratio is 1:1 is weighed, 4 '-diaminodiphenyl ethers are closed using dimethyl acetamide as solvent
The polyamic acid solution for being 10% at concentration then prepares 1% polyamic acid solution, and the nickel mangaic acid that 5g step (1) obtains is added
Lithium anode material powder stirs, and filters, dry, then in a nitrogen atmosphere in 100 DEG C, 200 DEG C, 300 DEG C, 450 DEG C of each processing
1 ~ 2h carries out hot imide reaction, obtains the modified nickel ion doped material of polyimides cladding, Dopants.
The beneficial effects of adopting the technical scheme are that
It is forthright again that it can be improved by halogen family ion substitution part negative oxygen ion using halogen family modification by ion-doping in the present invention
Energy and cycle performance.Polyimides have excellent hot property, dielectric properties and mechanical property etc. become electronics, chemical industry and
The widely used high molecular material in the fields such as space flight.Certain density polyamic acid is prepared by chemically synthesized method, then
Hot imide reaction occurs on the nickel lithium manganate cathode material surface of Dopants using polyamic acid, may be implemented pair
Material uniformly completely coats, avoid nickel ion doped directly and electrolyte contacts, be conducive to nickel lithium manganate cathode material globality
The promotion of energy, the present invention obtain modified nickel in such a way that halogen ion doping vario-property and surface polyimides coating modification combine
Lithium manganate material, capacity retention ratio is 90.8% under room temperature after recycling 200 times under 1C multiplying power, capacity retention ratio at 55 DEG C of high temperature
It is 88.5%, greatly improves specific capacity and stable circulation performance under nickel lithium manganate cathode material room temperature and high temperature.
Halogen of the present invention, using ethyl alcohol or water as solvent, carries out being sufficiently mixed dispersion, and pass through control by way of sand milling
Maturing temperature processed and time have obtained the nickel ion doped material of the stable halide ion doping of uniform particle sizes, performance.
The additional amount for the nickel ion doped material that the present invention is adulterated by the concentration and halide ion of control polyamic acid solution,
And time and the temperature of polymerization reaction are controlled, realize uniformly cladding.
Detailed description of the invention
It, below will be to specific in order to illustrate more clearly of the specific embodiment of the invention or technical solution in the prior art
Embodiment or attached drawing needed to be used in the description of the prior art be briefly described, it should be apparent that, it is described below
Attached drawing is some embodiments of the present invention, for those of ordinary skill in the art, before not making the creative labor
It puts, can also be obtained according to these attached drawings other attached drawings.
The scanning for the nickel ion doped material that Fig. 1 is modified for the polyimides cladding of the embodiment of the present invention 1, Dopants
Electron microscope.
Fig. 2 is the modified nickel ion doped material of the polyimides cladding of the embodiment of the present invention 1, Dopants in 2C
Cycle performance curve under multiplying power.
The multiplying power for the nickel ion doped material that Fig. 3 is modified for the polyimides cladding of the embodiment of the present invention 1, Dopants
Performance test curve.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, invention is carried out combined with specific embodiments below
Clear, complete description.
The nickel ion doped material of 1 polyimides of embodiment cladding, fluorine element doping vario-property
A kind of polyimides cladding, fluorine element doping vario-property nickel ion doped material preparation method comprising following steps:
(1) lithium carbonate 3.879g, manganese dioxide 14.490g, nickel oxide 3.773g and the ammonium fluoride of stoichiometric ratio are weighed
0.151g is put into the small sand milling jar of 100mL, and using 70mL dehydrated alcohol as solvent, 2h is sanded in 2000 turns/min revolving speed, will be obtained
Mixture put in an oven in 105 DEG C dry, be then sintered 9h at 900 DEG C, obtain the nickel ion doped of Fluorin doped
(LiNi0.5Mn1.5O3.96F0.04) positive electrode.
(2) using dimethyl acetamide as solvent 25mL, the polyamic acid solution that compound concentration is 1% is stirred under argon atmosphere
The nickel lithium manganate cathode material that 5g step (1) obtains is added in 1h, is ultrasonically treated 10min, supersonic frequency 20KHz, temperature 35
DEG C, filter, 4h is dried under reduced pressure under the conditions of 40 DEG C, then in a nitrogen atmosphere in 100 DEG C, 200 DEG C, 300 DEG C, 450 DEG C everywhere
1.5h is managed, the nickel ion doped material of polyimides cladding, fluorine element doping vario-property is obtained.
Through electro-chemical test, obtained polyimides is coated, the nickel ion doped material of fluorine element doping vario-property is in 0.2C
Under multiplying power, first discharge specific capacity 142.2mAh/g, after recycling 200 times under 1C multiplying power, specific capacity is 126.9 mAh/g,
Conservation rate is 93.2%.
The nickel ion doped material of 2 polyimides of embodiment cladding, bromo element doping vario-property
(1) lithium carbonate 3.879g, manganese dioxide 14.490g, nickel oxide 3.773g and the ammonium bromide of stoichiometric ratio are weighed
0.392g is put into the small sand milling jar of 100mL, and using 70mL water as solvent, 2h, the mixing that will be obtained is sanded in 2000 turns/min revolving speed
Object is put dries in 105 DEG C in an oven, is then sintered 9h at 900 DEG C, obtains the nickel ion doped of bromine doping
(LiNi0.5Mn1.5O3.96Br0.04) positive electrode.
(2) using 25mL dimethyl acetamide as solvent, the polyamic acid solution that compound concentration is 1%, argon atmosphere stirs 1h
Afterwards, the nickel lithium manganate cathode material that 5 g steps (1) obtain is added, is ultrasonically treated 10min, supersonic frequency 20KHz, temperature is
35 DEG C, filter, 4h be dried under reduced pressure under the conditions of 40 DEG C, then in a nitrogen atmosphere in 100 DEG C, 200 DEG C, 300 DEG C, 450 DEG C it is each
1h is handled, the nickel ion doped material of polyimides cladding, bromo element doping vario-property is obtained.
Through electro-chemical test, obtained polyimides is coated, the nickel ion doped material of bromo element doping vario-property is in 0.2C
Under multiplying power, first discharge specific capacity 137.0mAh/g, after recycling 200 times under 1C multiplying power, specific capacity is 122.3 mAh/g,
Conservation rate is 90.8%.
The nickel ion doped material of 3 polyimides of embodiment cladding, chlorine element doping vario-property
(1) lithium carbonate 3.879g, manganese dioxide 14.490g, nickel oxide 3.773g and the ammonium chloride of stoichiometric ratio are weighed
0.214g is put into the small sand milling jar of 100mL, and using 70mL dehydrated alcohol as solvent, 2h is sanded in 2000 turns/min revolving speed, will be obtained
Mixture put in an oven in 105 DEG C dry, be then sintered 9h at 900 DEG C, obtain chlorine doping nickel ion doped
(LiNi0.5Mn1.5O3.96Cl0.04) positive electrode.
(2) using 25mL dimethyl acetamide as solvent, the polyamic acid solution that compound concentration is 1%, argon atmosphere stirs 1h
Afterwards, the nickel lithium manganate cathode material powder that 5g step (1) obtains is added, is ultrasonically treated 10min, supersonic frequency 20KHz, temperature
It is 35 DEG C, filters, 4h is dried under reduced pressure under the conditions of 35 DEG C, then in a nitrogen atmosphere in 100 DEG C, 200 DEG C, 300 DEG C, 450 DEG C
Each processing 2h, obtains the nickel ion doped material of polyimides cladding, chlorine element doping vario-property.
Through electro-chemical test, obtained polyimides is coated, the nickel ion doped material of chlorine element doping vario-property is in 0.2C
Under multiplying power, first discharge specific capacity 140.0mAh/g, after recycling 200 times under 1C multiplying power, specific capacity is 124.0 mAh/g,
Conservation rate is 91.9%.
1 fluorine element doping vario-property of test example, the performance study of the nickel ion doped material of different coating modifications
The nickel ion doped material of experiment 1-1 polyimides cladding, fluorine element doping vario-property:
A kind of preparation method of the nickel ion doped material of polyimides cladding fluorine element doping vario-property comprising following steps:
(1) lithium carbonate 3.879g, manganese dioxide 14.490g, nickel oxide 3.773g and the ammonium fluoride of stoichiometric ratio are weighed
0.151g is put into the small sand milling tank of 100mL, and using 70mL dehydrated alcohol as solvent, 2h is sanded in 2000 turns/min revolving speed, by what is obtained
Mixture is put dries in 105 DEG C in an oven, is then sintered 9h at 900 DEG C, obtains the nickel ion doped of Fluorin doped
(LiNi0.5Mn1.5O3.96F0.04) positive electrode powder.
(2) using 25mL dimethyl acetamide as solvent, the polyamic acid solution that compound concentration is 1%, argon atmosphere stirs 1h
Afterwards, the nickel lithium manganate cathode material powder that 5g step (1) obtains is added, is ultrasonically treated 10min, supersonic frequency 20KHz, temperature
It is 35 DEG C, filters, 4h is dried under reduced pressure under the conditions of 40 DEG C, then in a nitrogen atmosphere in 100 DEG C, 200 DEG C, 300 DEG C, 450 DEG C
1 ~ 2h of each processing obtains the nickel ion doped material of polyimides cladding, fluorine element doping vario-property.
The nickel ion doped material of experiment 1-2 carbon coating fluorine element doping vario-property:
A kind of preparation method of the nickel ion doped material of carbon coating fluorine element doping vario-property comprising following steps:
(1) lithium carbonate 3.879g, manganese dioxide 14.490g, nickel oxide 3.773g and the ammonium fluoride of stoichiometric ratio are weighed
0.151g is put into the small sand milling jar of 100mL, and using 70m dehydrated alcohol as solvent, 2h is sanded in 2000 turns/min revolving speed, by what is obtained
Mixture is put dries in 105 DEG C in an oven, is then sintered 9h at 900 DEG C, obtains the nickel ion doped of Fluorin doped
(LiNi0.5Mn1.5O3.96F0.04) positive electrode.
(2) by 1g Gelatin in 100mL deionized water, then in 50 DEG C of stirring 2h, 0.05g carbon black is then added
With the nickel ion doped (LiNi of 5g Fluorin doped0.5Mn1.5O3.96F0.04) positive electrode, subsequent ultrasonic disperse 30min exists mixture
50 DEG C of stirring 1h, then filter mixture, dry in an oven in 105 DEG C, are then sintered 3h at 300 DEG C, obtain carbon packet
Fluorin doped nickel ion doped (the LiNi covered0.5Mn1.5O3.96F0.04) positive electrode.
The nickel ion doped material of test example 1-3 alumina-coated bromo element doping vario-property:
A kind of preparation method of the nickel ion doped material of alumina-coated fluorine element doping vario-property comprising following steps:
(1) lithium carbonate 3.879g, manganese dioxide 14.490g, nickel oxide 3.773g and the ammonium fluoride of stoichiometric ratio are weighed
0.151g is put into the small sand milling jar of 100mL, and using 70mL dehydrated alcohol as solvent, 2h is sanded in 2000 turns/min revolving speed, will be obtained
Mixture put in an oven in 105 DEG C dry, be then sintered 9h at 900 DEG C, obtain the nickel ion doped of Fluorin doped
(LiNi0.5Mn1.5O3.96F0.04) positive electrode.
(2) aluminium isopropoxide 0.10g is then added to 60 DEG C or so in heating water bath 30mL dehydrated alcohol, stirs 20min, to
Aluminium isopropoxide all dissolves, and the nickel ion doped (LiNi of 5g Fluorin doped is added0.5Mn1.5O3.96F0.04) positive electrode, continue to stir
1h then heats to 70 DEG C, and stirring is evaporated, and obtained mixture is put and is dried in an oven in 105 DEG C, then at 400 DEG C
It is sintered 3h, obtains the Fluorin doped nickel ion doped (LiNi of alumina-coated0.5Mn1.5O3.96F0.04) positive electrode.
Effect example 1: the product under each test in test example 1 is subjected to electrochemical property test, is specifically shown in Table 1:
Table 1: the electrochemical property test of test example 1
It can be obtained by experimental result and recycle 200 capacity retention ratios under the 1C multiplying power of test example 1 and be far longer than test example 1-2 and test
Example 1-3.
The experimental condition of the nickel ion doped material of 2 fluorine element doping vario-property of test example is studied
Test example 2-1:
A kind of polyimides cladding, fluorine element doping vario-property nickel ion doped material preparation method comprising following steps:
(1) lithium carbonate 3.879g, manganese dioxide 14.490g, nickel oxide 3.773g and the ammonium fluoride of stoichiometric ratio are weighed
0.151g is put into the small sand milling tank of 100mL, and using 70mL dehydrated alcohol as solvent, 2h is sanded in 2000 turns/min revolving speed, by what is obtained
Mixture is put dries in 105 DEG C in an oven, is then sintered 9h at 900 DEG C, obtains the nickel ion doped of Fluorin doped
(LiNi0.5Mn1.5O3.96F0.04) positive electrode.
(2) using 25mL dimethyl acetamide as solvent, the polyamic acid solution that compound concentration is 1%, argon atmosphere stirs 1h
Afterwards, the nickel lithium manganate cathode material powder that 5 g steps (1) obtain is added, is ultrasonically treated 10min, supersonic frequency 20KHz, temperature
Degree is 35 DEG C, filters, 4h is dried under reduced pressure under the conditions of 40 DEG C, then in a nitrogen atmosphere in 100 DEG C, 200 DEG C, 300 DEG C, 450
DEG C 1 ~ 2h of each processing, obtains the nickel ion doped material of polyimides cladding, fluorine element doping vario-property.
Test example 2-2:
A kind of polyimides cladding, fluorine element doping vario-property nickel ion doped material preparation method comprising following steps:
(1) 3.879g lithium carbonate, 11.441g mangano-manganic oxide, 3.773g nickel oxide and the 0.1038g fluorine of stoichiometric ratio are weighed
Change lithium to be put into the small sand milling tank of 100mL, using 70mL dehydrated alcohol as solvent, 2h is sanded in 2000 turns/min revolving speed, mixed by what is obtained
It closes object to put in an oven in 105 DEG C of drying, is then sintered 9h at 900 DEG C, obtains the nickel ion doped of Fluorin doped
(LiNi0.5Mn1.5O3.96F0.04) positive electrode.
(2) using dimethyl acetamide as solvent 25mL, the polyamic acid solution that compound concentration is 1%, argon atmosphere stirs 1h
Afterwards, the nickel lithium manganate cathode material powder that 5g step (1) obtains is added, is ultrasonically treated 10min, supersonic frequency 20KHz, temperature
It is 35 DEG C, filters, 4h is dried under reduced pressure under the conditions of 40 DEG C, then in a nitrogen atmosphere in 100 DEG C, 200 DEG C, 300 DEG C, 450 DEG C
1 ~ 2h of each processing obtains the nickel ion doped material of polyimides cladding, fluorine element doping vario-property.
Test example 2-3:
A kind of polyimides cladding, fluorine element doping vario-property nickel ion doped material preparation method comprising following steps:
(1) lithium carbonate 3.879g, manganese dioxide 14.490g, nickel oxide 3.773g and the ammonium fluoride of stoichiometric ratio are weighed
0.151g is put into the small sand milling tank of 100mL, and using 70mL dehydrated alcohol as solvent, 2h is sanded in 2000 turns/min revolving speed, by what is obtained
Mixture is put dries in 105 DEG C in an oven, is then sintered 10h at 800 DEG C, obtains the nickel ion doped of Fluorin doped
(LiNi0.5Mn1.5O3.96F0.04) positive electrode.
(2) with dimethyl acetamide (25mL) for solvent, the polyamic acid solution that compound concentration is 1%, argon atmosphere stirring
After 1h, the nickel lithium manganate cathode material powder (5 g) that step (1) obtains is added, is ultrasonically treated 10min, supersonic frequency is
20KHz, temperature be 35 DEG C, filter, 4h is dried under reduced pressure under the conditions of 35 DEG C, then in a nitrogen atmosphere in 100 DEG C, 200 DEG C,
300 DEG C, 450 DEG C of 1 ~ 2h of each processing, obtain the nickel ion doped material of polyimides cladding, fluorine element doping vario-property.
Test example 2-4:
A kind of polyimides cladding, fluorine element doping vario-property nickel ion doped material preparation method comprising following steps:
(1) lithium carbonate 3.879g, manganese dioxide 14.490g, nickel oxide 3.773g and the ammonium fluoride of stoichiometric ratio are weighed
0.151g is put into 500mL ball grinder, using dehydrated alcohol as solvent, 300 turns/min revolving speed ball milling 10h, and the mixture that will be obtained
It puts and is dried in an oven in 105 DEG C, be then sintered 9h at 900 DEG C, the nickel ion doped of Fluorin doped will be obtained
(LiNi0.5Mn1.5O3.96F0.04) positive electrode.
(2) using 25mL dimethyl acetamide as solvent, the polyamic acid solution that compound concentration is 1%, argon atmosphere stirs 1h
Afterwards, the nickel lithium manganate cathode material powder that 5g step (1) obtains is added, is ultrasonically treated 10min, supersonic frequency 20KHz, temperature
It is 35 DEG C, filters, 4h is dried under reduced pressure under the conditions of 35 DEG C, then in a nitrogen atmosphere in 100 DEG C, 200 DEG C, 300 DEG C, 450 DEG C
1 ~ 2h of each processing obtains the nickel ion doped material of polyimides cladding, fluorine element doping vario-property.
Measure of merit 2
Product under each test in test example 2 is subjected to electrochemical property test, is specifically shown in Table 2:
The electrochemical property test of 2 test example 2 of table
It can be obtained by experimental result and recycle 200 capacity retention ratios under the 1C multiplying power of test example 2-1 and be far longer than test example 2-2,2-3
And 2-4.
The experimental condition of the nickel ion doped material of 3 polyimides coating modification of test example is studied
Test example 3-1
A kind of polyimides cladding, fluorine element doping vario-property nickel ion doped material preparation method comprising following steps:
(1) lithium carbonate 3.879g, manganese dioxide 14.490g, nickel oxide 3.773g and the ammonium fluoride of stoichiometric ratio are weighed
0.151g is put into the small sand milling jar of 100mL, and using 70mL dehydrated alcohol as solvent, 2h is sanded in 2000 turns/min revolving speed, will be obtained
Mixture put in an oven in 105 DEG C dry, be then sintered 9h at 900 DEG C, obtain the nickel ion doped of Fluorin doped
(LiNi0.5Mn1.5O3.96F0.04) positive electrode.
(2) using dimethyl acetamide as solvent 25mL, the polyamic acid solution that compound concentration is 1% is stirred under argon atmosphere
The nickel lithium manganate cathode material that 5g step (1) obtains is added in 1h, is ultrasonically treated 10min, supersonic frequency 20KHz, temperature 35
DEG C, filter, 4h is dried under reduced pressure under the conditions of 40 DEG C, then in a nitrogen atmosphere in 100 DEG C, 200 DEG C, 300 DEG C, 450 DEG C everywhere
1h is managed, the nickel ion doped material of polyimides cladding, fluorine element doping vario-property is obtained.
Test example 3-2
A kind of polyimides cladding, fluorine element doping vario-property nickel ion doped material preparation method comprising following steps:
(1) lithium carbonate 3.879g, manganese dioxide 14.490g, nickel oxide 3.773g and the ammonium fluoride of stoichiometric ratio are weighed
0.151g is put into the small sand milling jar of 100mL, and using 70mL dehydrated alcohol as solvent, 2h is sanded in 2000 turns/min revolving speed, will be obtained
Mixture put in an oven in 105 DEG C dry, be then sintered 9h at 900 DEG C, obtain the nickel ion doped of Fluorin doped
(LiNi0.5Mn1.5O3.96F0.04) positive electrode.
(2) using dimethyl acetamide as solvent 25mL, the polyamic acid solution that compound concentration is 1.5% is stirred under argon atmosphere
1h is mixed, the nickel lithium manganate cathode material that 5g step (1) obtains is added, is ultrasonically treated 10min, supersonic frequency 20KHz, temperature is
35 DEG C, filter, 4h be dried under reduced pressure under the conditions of 40 DEG C, then in a nitrogen atmosphere in 100 DEG C, 200 DEG C, 300 DEG C, 450 DEG C it is each
1h is handled, the nickel ion doped material of polyimides cladding, fluorine element doping vario-property is obtained.
Test example 3-3
A kind of polyimides cladding, fluorine element doping vario-property nickel ion doped material preparation method comprising following steps:
(1) lithium carbonate 3.879g, manganese dioxide 14.490g, nickel oxide 3.773g and the ammonium fluoride of stoichiometric ratio are weighed
0.151g is put into the small sand milling jar of 100mL, and using 70mL dehydrated alcohol as solvent, 2h is sanded in 2000 turns/min revolving speed, will be obtained
Mixture put in an oven in 105 DEG C dry, be then sintered 9h at 900 DEG C, obtain the nickel ion doped of Fluorin doped
(LiNi0.5Mn1.5O3.96F0.04) positive electrode.
(2) using dimethyl acetamide as solvent 25mL, the polyamic acid solution that compound concentration is 0.5% is stirred under argon atmosphere
1h is mixed, the nickel lithium manganate cathode material that 5g step (1) obtains is added, is ultrasonically treated 10min, supersonic frequency 20KHz, temperature is
35 DEG C, filter, 4h be dried under reduced pressure under the conditions of 40 DEG C, then in a nitrogen atmosphere in 100 DEG C, 200 DEG C, 300 DEG C, 450 DEG C it is each
1h is handled, the nickel ion doped material of polyimides cladding, fluorine element doping vario-property is obtained.
Test example 3-4
A kind of polyimides cladding, fluorine element doping vario-property nickel ion doped material preparation method comprising following steps:
(1) lithium carbonate 3.879g, manganese dioxide 14.490g, nickel oxide 3.773g and the ammonium fluoride of stoichiometric ratio are weighed
0.151g is put into the small sand milling jar of 100mL, and using 70mL dehydrated alcohol as solvent, 2h is sanded in 2000 turns/min revolving speed, will be obtained
Mixture put in an oven in 105 DEG C dry, be then sintered 9h at 900 DEG C, obtain the nickel ion doped of Fluorin doped
(LiNi0.5Mn1.5O3.96F0.04) positive electrode.
(2) using dimethyl acetamide as solvent 25mL, the polyamic acid solution that compound concentration is 1% is stirred under argon atmosphere
The nickel lithium manganate cathode material that 5g step (1) obtains is added in 1h, is ultrasonically treated 10min, supersonic frequency 20KHz, temperature 35
DEG C, it filters, 4h is dried under reduced pressure under the conditions of 40 DEG C, then in a nitrogen atmosphere in 60 DEG C of processing 30min, 120 DEG C of processing
30min, 200 DEG C of processing 1h, 300 DEG C of processing 1h, 400 DEG C of processing 10min obtain polyimides cladding, fluorine element doping vario-property
Nickel ion doped material.
Measure of merit 3
Product under each test in test example 3 is subjected to electrochemical property test, is specifically shown in Table 3:
The electrochemical property test of 3 test example 3 of table
It can be obtained by experimental result and recycle 200 capacity retention ratios under the 1C multiplying power of test example 3-1 and be far longer than test example 3-2,3-3
And 3-4.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify to technical solution documented by previous embodiment or equivalent replacement of some of the technical features；And
These are modified or replaceed, the spirit and model of technical solution of the embodiment of the present invention that it does not separate the essence of the corresponding technical solution
It encloses.
Claims (10)
1. a kind of preparation method of the modified nickel ion doped material of polyimides cladding, Dopants, which is characterized in that its
Include the following steps:
(1) lithium carbonate, manganese dioxide, nickel oxide and the ammonium halide of stoichiometric ratio are weighed, ethyl alcohol or water is added, grinding is mixed
It closes, obtained mixture is put and is dried in an oven, then sintering obtains the nickel lithium manganate cathode material of Dopants；
(2) the equal phthalic acid and 4 of stoichiometric ratio is weighed, 4 '-diaminodiphenyl ethers are closed using dimethyl acetamide as solvent
The polyamic acid solution for being 10% at concentration then prepares certain density polyamic acid solution, and the halogen that step (1) obtains is added
The nickel lithium manganate cathode material of race's element doping stirs, and filters, dry, and it is anti-then to carry out hot-imide in a nitrogen atmosphere
It answers, obtains the modified nickel ion doped material of polyimides cladding, Dopants；
The ammonium halide is selected from ammonium fluoride, ammonium chloride or ammonium bromide.
2. the preparation side of the modified nickel ion doped material of polyimides cladding according to claim 1, Dopants
Method, which is characterized in that molar ratio Li:Ni:Mn=1.05:0.5 of lithium carbonate, nickel oxide and manganese dioxide in the step (1):
1.5, the additional amount of ammonium halide is x moles (x=0.02,0.03,0.04 or 0.05), obtain the modified nickel manganese of Dopants
Sour lithium material LiNi0.5Mn1.5O4-xFX, LiNi0.5Mn1.5O4-xClX, LiNi0.5Mn1.5O4-xBrX。
3. the preparation side of the modified nickel ion doped material of polyimides cladding according to claim 1, Dopants
Method, which is characterized in that ground and mixed in the step (1), to be sanded mixing, sands milling revolving speed is 2000 turns/min, the time for 1 ~
3h。
4. the preparation method of the nickel ion doped material of polyimides cladding Dopants according to claim 1,
It is characterized in that, drying temperature is 105 ± 2 DEG C in the step (1).
5. the preparation side of the modified nickel ion doped material of polyimides cladding according to claim 1, Dopants
Method, which is characterized in that sintering temperature is 900 DEG C in the step (1), is sintered 7 ~ 10h.
6. the preparation side of the modified nickel ion doped material of polyimides cladding according to claim 1, Dopants
Method, which is characterized in that a certain concentration is 1% polyamic acid solution in the step (2).
7. the preparation side of the modified nickel ion doped material of polyimides cladding according to claim 1, Dopants
Method, which is characterized in that the additional amount of nickel lithium manganate cathode material powder is 5g in the step (2).
8. the preparation side of the modified nickel ion doped material of polyimides cladding according to claim 1, Dopants
Method, which is characterized in that in the step (2) temperature of heat Asia amidation process be 100 DEG C, 200 DEG C, 300 DEG C, 450 DEG C it is each
Handle 1 ~ 2h.
9. the preparation method of the nickel ion doped material of polyimides cladding Dopants according to claim 1,
It is characterized in that, drying condition in the step (2) are as follows: 40 ± 5 DEG C of vacuum drying 4h.
10. the preparation method of the nickel ion doped material of polyimides cladding Dopants according to claim 1,
It is characterized in that,
(1) weigh the lithium carbonate, manganese dioxide and nickel oxide of molar ratio Li:Ni:Mn=1.05:0.5:1.5, be added x moles (x=
0.01,0.02,0.03 or NH 0.04)4Ethyl alcohol or water is added in F, and 1 ~ 3h of mixing is sanded, and sand milling revolving speed is 2000 turns/min,
Obtained mixture is put and is dried in an oven, 7 ~ 10h is sintered at 900 DEG C and obtains the nickel ion doped anode of Dopants
Material powder LiNi0.5Mn1.5O4-xAX, A is selected from F, Cl or Br；
(2) the equal phthalic acid and 4 of stoichiometric ratio is weighed, 4 '-diaminodiphenyl ethers are closed using dimethyl acetamide as solvent
The polyamic acid solution for being 10% at concentration then prepares 1% polyamic acid solution, and the nickel mangaic acid that 5g step (1) obtains is added
Lithium anode material powder stirs, and filters, dry, then in a nitrogen atmosphere in 100 DEG C, 200 DEG C, 300 DEG C, 450 DEG C of each processing
1 ~ 2h carries out hot imide reaction, obtains the modified nickel ion doped material of polyimides cladding, Dopants.
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| CN112447959A (en) * | 2020-12-10 | 2021-03-05 | 山东丰元化学股份有限公司 | Surface treatment method of high-nickel ternary cathode material |
| CN112447959B (en) * | 2020-12-10 | 2022-07-08 | 山东丰元化学股份有限公司 | Surface treatment method of high-nickel ternary cathode material |
| CN112670451A (en) * | 2020-12-29 | 2021-04-16 | 西北工业大学 | Preparation method of organic composite positive electrode for improving energy density of lithium-manganese battery for underwater vehicle |
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