CN106549147A - Nickle cobalt lithium manganate that a kind of two-dimension nano materials are fixed and preparation method and application - Google Patents
Nickle cobalt lithium manganate that a kind of two-dimension nano materials are fixed and preparation method and application Download PDFInfo
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Abstract
The invention provides a kind of nickle cobalt lithium manganate of two-dimension nano materials fixation and preparation method and application.The nickle cobalt lithium manganate that the two-dimension nano materials are fixed is to be stacked to be composited by two-dimension nano materials with the nickle cobalt lithium manganate of spherical structure in interlayer mode, and the nickle cobalt lithium manganate of spherical structure is piled up with the pattern of Rotating fields in the template of two-dimension nano materials.Tightly packed, tap density and energy density of the raising nickle cobalt lithium manganate as positive electrode can be realized；And the nickle cobalt lithium manganate surface of spherical structure is smooth, specific surface area is low, it is possible to reduce the generation with electrolyte side reaction, the first charge-discharge efficiency of lithium ion battery is improved；Nickle cobalt lithium manganate in the template of two-dimension nano materials is piled up to form secondary spherical particle with the pattern of Rotating fields, and the two-dimension nano materials can suppress Li+There is the defect of dislocation in the layered structure during deintercalation, further improve the deintercalation ability of lithium ion, and the electric conductivity of nickle cobalt lithium manganate can be improved and improve its charge-discharge performance.
Description
Technical field
The invention belongs to anode material for lithium-ion batteries technical field, is related to the nickel cobalt manganese that a kind of two-dimension nano materials are fixed
Sour lithium and preparation method and application.
Background technology
With the fast development of power vehicle, lithium ion battery occupies leading position in power vehicle.In lithium ion
In electrokinetic cell industrialization promotion, the requirement to battery capacity, safety, integrated cost is higher, and positive electrode becomes main bottle
Neck.At present, anode material for lithium-ion batteries mainly has cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, nickle cobalt lithium manganate ternary
Deng.Wherein LiFePO4（LiFePO4）Had a safety feature with which, cycle performance is excellent, environmental friendliness, abundant raw material source, into
This low advantage and become the main positive electrode of lithium ion battery.However, LiFePO4（LiFePO4）As lithium battery anode
Material, however it remains defect, the electronic conductivity for being mainly manifested in LiFePO4 is poor, chargeable voltage is relatively low, low
Temperature stability is poor, tap density is little, the electric energy stored by unit volume battery is less.At present, the energy density of LiFePO4 reaches
Summit is arrived, improved space is little.New material substitution is had to look for, new-energy automobile power battery could obtain great prominent
It is broken.
Study, the relatively low theoretical gram volume of the specific energy of ferric phosphate lithium cell, only 170mAh/g, running voltage is
3.2V, and the theoretical gram volume of cobalt nickel lithium manganate ternary material is then 278mAh/g, running voltage is 3.65V, therefore nickel cobalt manganese
Ternary battery energy density is apparently higher than ferric phosphate lithium cell.Even so, nickel-cobalt-manganese ternary battery safety and cyclicity
Can be not as good as ferric phosphate lithium cell, this just constrains the range of application with high-energy-density ternary battery.Its maximum defect is
Self-heating occurs more than 180 DEG C, cyclical stability is poor.And LiFePO 4 material just occurs exothermic phenomenon for more than 250 DEG C.
When stratiform nickle cobalt lithium manganate is as tertiary cathode material, due to the cooperative effect of tri- kinds of elements of Ni, Co and Mn, tool
There are high specific discharge capacity, energy density height, cost relatively low and advantages of environment protection, combine LiCoO2, LiNiO2With
LiMnO2The advantage of three kinds of anode material for lithium-ion batteries, and performance is better than the positive electrode of any of the above one-component.The body
In system, the chemical property and physical property of material is different with the change of these three transition metal ratios.Introduce Ni,
Although being favorably improved the capacity of material, there is Li in stratiform cell positive material+There is dislocation with transition metal ionss
Trend, Ni2+Meeting and Li during too high levels+Mixing, cycle performance is deteriorated because of dislocation phenomenon.Introduce Co to reduce
Cation mixes occupy-place, and the layer structure of effective stabilizing material reduces resistance value, improves electrical conductivity, but when the increasing of Co ratios
It is big that to causing during certain limit, a and c reduces and c/a increases, capacity step-down.Mn is introduced, material cost not only can be reduced, and
And the safety and stability of material can also be improved.
But due to the restriction of its preparation technology and self structure performance, ternary material LiNi1/3Co1/3Mn1/3O2As lithium from
When sub- cell positive material is used, high rate performance still has sizable room for promotion.LiNi1/3Co1/3Mn1/3O2High rate performance compared with
Difference mainly has following reason：（1）LiNi1/3Co1/3Mn1/3O2It is a kind of ternary transition metal combined oxidation with layer structure
Thing crystalline material, is affected to be susceptible to " cation mixing ", i.e. LiNi by preparation technology1/3Co1/3Mn1/3O2In crystal structure
Part Ni2+Li can be occupied+Position, causes crystal partial structurtes to be caved in so that stability in the large reduction, affects the cyclicity of material
Energy, high rate performance；（2）Electrode material surface ion is easily dissolved in electrolyte in cyclic process, causes active substance
Loss；（3）The LiNi of existing market1/3Co1/3Mn1/3O2Tertiary cathode material in order to ensure product tap density, be compacted it is close
Degree, material crystals size are larger, cause electronics and the migration path of ion to increase, and LiNi1/3Co1/3Mn1/3O2As quasiconductor
Material own electronic electrical conductivity is relatively low（Belong to semi-conducting material）, so that its energy density is higher, power density is relatively low, i.e. multiplying power
Poor-performing.
Pin LiNi1/3Co1/3Mn1/3O2The poor problem of high rate performance, current research are concentrated mainly on preparation method wound
Newly, the aspect such as surface coating modification of modification by ion-doping and metal-oxide.In preparation method innovation, Rheological Phase Method is adapted to
Mix in solid and liquid, contribute to realizing the uniform mixing of presoma, although technique is very easy, it is desirable to relatively low, be adapted to
Industrialized production, but it has been short of in terms of control pattern；In terms of modification by ion-doping, current research is mainly by sun
The doping of ion equivalent state, the doping of cation non-equivalence state or the method such as anion doped improve the electronic conductance and ion-conductance of material
Lead, increase the stability of crystal structure, improve the output of lithium ion battery, although the partial electro chemical of battery can be improved
Performance, but the reunion of dopant ion causes the effect run counter to desire；The surface coating modification of metal-oxide is usually logical
Cross and one layer of suitable inert metal oxides material formation protective layer is coated in material surface, to reduce the active matter under high potential
Matter and the side reaction of electrolyte, keep structural stability of the material during repeated charge, improve the stable circulation of material
Property and high rate performance, but the electrical conductivity of material can be reduced, and technique is more complicated, the enforcement time of the technology is also longer.As in
State patent application CN201510659208.9, disclose a kind of nickle cobalt lithium manganate/graphene/carbon nano-tube composite positive pole and
Preparation method.Composite positive pole is by LiNi1/3Co1/3Mn1/3O2, Graphene and CNTs compositions, Graphene and CNTs institutes
The quality for accounting for very content is 10 for the mass ratio of 0.1%-20%, Graphene and CNTs:1-1:10；Its preparation method
For：With the stable suspension of Graphene and CNTs, nickel, cobalt, the acetate of manganese or nitrate and lithium carbonate are raw material, by stream
Covert method prepares nickle cobalt lithium manganate/graphene/carbon nano-tube composite positive pole.The technical step is more complicated, and raw material is more, when
Between it is longer, and need in technique strict controlling reaction temperature.
To sum up, being badly in need of one kind now at present can be to LiNi1/3Co1/3Mn1/3O2The method for carrying out suitable moditied processing, with
Effectively improve its high rate performance and cycle performance.
The content of the invention
In view of the shortcoming of above-mentioned prior art, it is an object of the invention to provide the nickel cobalt that a kind of two-dimension nano materials are fixed
LiMn2O4 and preparation method and application.The nickle cobalt lithium manganate that the two-dimension nano materials are fixed can make nickle cobalt lithium manganate in two dimension
Pile up to form secondary spherical particle with the pattern of Rotating fields in the template of nano material, and the two-dimension nano materials can suppress Li+There is the defect of dislocation in the layered structure during deintercalation.
In order to reach aforesaid goal of the invention, the present invention provides the nickle cobalt lithium manganate that a kind of two-dimension nano materials are fixed, its
It is to be stacked to be composited by two-dimension nano materials with the nickle cobalt lithium manganate of spherical structure in interlayer mode, the nickel of the spherical structure
Cobalt manganic acid lithium is piled up with the pattern of Rotating fields in the template of two-dimension nano materials.
In the nickle cobalt lithium manganate that above-mentioned two-dimension nano materials are fixed, it is preferable that the two-dimension nano materials include two sulfur
Change any one in tungsten, molybdenum bisuphide, stannic disulfide, silene.
In the nickle cobalt lithium manganate that above-mentioned two-dimension nano materials are fixed, it is preferable that the nickel that the two-dimension nano materials are fixed
The thickness of cobalt manganic acid lithium is 10nm-35nm.
The nickle cobalt lithium manganate that above-mentioned two-dimension nano materials are fixed has the spherical structure nickel cobalt of regular appearance, good fluidity
LiMn2O4, can realize tightly packed, greatly improve nickle cobalt lithium manganate as the tap density and energy density of positive electrode；And ball
The nickle cobalt lithium manganate surface of shape structure is smooth, specific surface area is low, it is possible to reduce the generation with electrolyte side reaction, improves lithium ion
The first charge-discharge efficiency of battery, additionally, nickle cobalt lithium manganate is piled up with the pattern of Rotating fields in the template of two-dimension nano materials
Secondary spherical particle is formed, the two-dimension nano materials can suppress Li+There is the defect of dislocation in the layered structure during deintercalation, enter
One step improves the deintercalation ability of lithium ion, and can improve the electric conductivity of nickle cobalt lithium manganate and improve its charge-discharge performance.
The present invention also provides the preparation method of the nickle cobalt lithium manganate that above-mentioned two-dimension nano materials are fixed, and which includes following step
Suddenly：
Step one：Nickel salt, cobalt salt and manganese salt are dissolved in deionized water with the stoichiometric proportion of nickle cobalt lithium manganate, be subsequently adding
Two-dimension nano materials mix as template, obtain suspension；
Step 2：Lithium salts is weighed by the mol ratio of lithium in the nickle cobalt lithium manganate, dissolving in deionized water, obtains lithium salts molten
Liquid；
Step 3：The lithium salt solution is added drop-wise in the suspension, is stirred in Deca, its mixing speed is 2500-
5000rpm, then sucking filtration, and 10h-16h is vacuum dried at 80 DEG C -100 DEG C, obtain powder；
Step 4：By the powder mull, it is subsequently placed in shielding gas in 700 DEG C of -800 DEG C of temperature lower calcination 4h-6h, obtains two
The nickle cobalt lithium manganate that dimension nano material is fixed；
Wherein, the two-dimension nano materials with the mol ratio of lithium salts are（1-5）：1.
In above-mentioned preparation method, it is preferable that in the nickel salt, cobalt salt, manganese salt and lithium salts, at least a kind of is nitric acid
Salt or acetate.
In above-mentioned preparation method, it is preferable that the nickel salt includes nickel sulfate, nickel nitrate, nickel acetate, citric acid nickel, ammonia
The combination of one or more in base nickel sulphonic acid and nickel halogenide.
In above-mentioned preparation method, it is preferable that the cobalt salt includes cobaltous sulfate, cobalt acetate, cobalt nitrate, citric acid cobalt, halogen
Change the combination of one or more in cobalt.
In above-mentioned preparation method, it is preferable that the manganese salt includes manganese sulfate, manganese acetate, manganese nitrate, manganese citrate and halogen
Change the combination of one or more in manganese.
In above-mentioned preparation method, it is preferable that the lithium salts includes lithium carbonate, lithium sulfate, lithium nitrate, Quilonorm (SKB), Fructus Citri Limoniae
The combination of one or more in sour lithium and lithium halide.
In above-mentioned preparation method, it is preferable that in the suspension, the total mass concentration of nickel salt, cobalt salt and manganese salt is 50
G/L -70g/L, in the lithium salt solution, the mass concentration of lithium salts is 5 g/L -10g/L.
Above-mentioned preparation method, in the preparation process of cobalt nickel lithium manganate ternary material, introduces two-dimension nano materials（Curing
Tungsten, molybdenum bisuphide, stannic disulfide, silene）Used as template, nickle cobalt lithium manganate is in the template of two-dimension nano materials with Rotating fields
Pattern pile up to form secondary spherical particle, form the nickle cobalt lithium manganate fixed by two-dimension nano materials, it is similar to be layering
Shape.The two-dimension nano materials can suppress Li+There is the defect of dislocation in the layered structure during deintercalation, further improve lithium ion
Deintercalation ability, and the electric conductivity of nickle cobalt lithium manganate can be improved and improve its charge-discharge performance.Mix with traditional ion
Miscellaneous modified and surface coating modification etc. is compared, and the nickle cobalt lithium manganate of the two-dimension nano materials fixation that the preparation method is obtained is more equal
It is even, steady quality.The electric conductivity and quality stability of current ferric phosphate lithium cell can be substantially improved.
The present invention also provides the lithium ion battery of the nickle cobalt lithium manganate as positive electrode of above-mentioned two-dimension nano materials fixation.
It is described that the lithium ion battery includes that battery case, pole piece and electrolyte, the pole piece and electrolyte are sealingly received within
In battery case, the pole piece includes positive pole, negative pole and the barrier film between positive pole and negative pole, the positive pole include collector and
Load positive electrode on a current collector, the negative pole include collector and load negative material on a current collector, it is described just
Pole material is the nickle cobalt lithium manganate that the two-dimension nano materials are fixed.
Nickle cobalt lithium manganate that a kind of two-dimension nano materials that the present invention is provided are fixed and preparation method and application, it is and existing
Technology is compared, its protrusion the characteristics of and excellent effect be：
（1）The present invention provide two-dimension nano materials fix nickle cobalt lithium manganate have regular appearance, good fluidity it is spherical
Structure nickle cobalt lithium manganate, can realize tightly packed, greatly improve nickle cobalt lithium manganate as the tap density and energy of positive electrode
Density；And the nickle cobalt lithium manganate surface of spherical structure is smooth, specific surface area is low, it is possible to reduce the generation with electrolyte side reaction,
Improve lithium ion battery first charge-discharge efficiency, additionally, nickle cobalt lithium manganate in the template of two-dimension nano materials with Rotating fields
Pattern pile up to form secondary spherical particle, the two-dimension nano materials can suppress Li+There is position in the layered structure during deintercalation
Wrong defect, further improves the deintercalation ability of lithium ion, and can improve the electric conductivity of nickle cobalt lithium manganate and improve its charge and discharge
Electric cycle performance；
（2）The preparation method of the nickle cobalt lithium manganate that the two-dimension nano materials that the present invention is provided are fixed is in cobalt nickel lithium manganate ternary material
Preparation process in, introduce two-dimension nano materials（Tungsten disulfide, molybdenum bisuphide, stannic disulfide, silene）As template, formed
The nickle cobalt lithium manganate fixed by two-dimension nano materials, the similar shape that is layering.Wrap with traditional modification by ion-doping and surface
Cover it is modified etc. compare, the nickle cobalt lithium manganate that two-dimension nano materials that the preparation method is obtained are fixed is more uniformly distributed, steady quality.Energy
The electric conductivity and high temperature quality stability of current ferric phosphate lithium cell is substantially improved；
（3）The lithium ion battery that the present invention is provided is adopted by the nickle cobalt lithium manganate of two-dimension nano materials and spherical structure with interlayer side
The nickle cobalt lithium manganate that the two-dimension nano materials that formula is composited are fixed improves nickel-cobalt lithium manganate cathode material as positive electrode
Charge-discharge performance.
Specific embodiment
Below by way of specific embodiment, the present invention is described in further detail, but this should not be interpreted as the present invention
Scope be only limitted to Examples below.In the case of without departing from said method thought of the present invention, according to ordinary skill
Various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A kind of preparation method of the nickle cobalt lithium manganate that molybdenum bisuphide is fixed is present embodiments provided, which comprises the following steps：
Step one：1mol nickel acetates, 1mol cobalt acetates and 1mol manganese acetates are dissolved in 50ml deionized waters, are sufficiently stirred for,
1mol molybdenum bisuphide is subsequently adding as template, 60min is stirred, is obtained suspension；
Step 2：3mol Quilonorm (SKB) is weighed, is sufficiently stirred for being dissolved in 100ml deionized waters, is obtained lithium acetate solution；
Step 3：Lithium acetate solution is added drop-wise in above-mentioned suspension with the speed of 20m1/min, is stirred in Deca, its stirring
Speed is 2500rpm, then 2. 5h are stirred at room temperature, then sucking filtration, and at 100 DEG C is vacuum dried 16h, obtains powder；
Step 4：15min will be ground in the powder dry environment, it is subsequently placed in tube furnace, 800 DEG C under argon protection
Temperature lower calcination 4h, obtains the nickle cobalt lithium manganate of molybdenum bisuphide fixation.
The nickle cobalt lithium manganate that molybdenum bisuphide fixation is obtained to the present embodiment is tested, and finds the nickel that the molybdenum bisuphide is fixed
The average thickness of cobalt manganic acid lithium is 20nm, and the nickle cobalt lithium manganate of the molybdenum bisuphide by layer structure and spherical structure is with interlayer side
Formula stacking is composited, and the nickle cobalt lithium manganate of the spherical structure is piled up with the pattern of Rotating fields in the template of molybdenum bisuphide.
The nickle cobalt lithium manganate that the present embodiment is obtained molybdenum bisuphide fixation makes knob as the positive electrode of lithium ion battery
Fastening lithium ionic cell, in the lithium ion battery lithium ion battery, under 0.1C multiplying powers, specific discharge capacity is 220 mAh/g, 10C
Under multiplying power, specific discharge capacity is 210 mAh/g.
Embodiment 2
A kind of preparation method of the nickle cobalt lithium manganate that tungsten disulfide is fixed is present embodiments provided, which comprises the following steps：
Step one：1mol nickel sulfate, 1mol cobaltous sulfates and 1mol manganese sulfates are dissolved in 50ml deionized waters, are sufficiently stirred for,
1mol tungsten disulfides are subsequently adding as template, 60min are stirred, is obtained suspension；
Step 2：3mol Quilonorm (SKB) is weighed, is sufficiently stirred for being dissolved in 100ml deionized waters, is obtained lithium acetate solution；
Step 3：Lithium acetate solution is added drop-wise in above-mentioned suspension with the speed of 20m1/min, is stirred in Deca, its stirring
Speed is 3000rpm, then 2.5h is stirred at room temperature, then sucking filtration, and at 100 DEG C is vacuum dried 12h, obtains powder；
Step 4：15min will be ground in the powder dry environment, it is subsequently placed in tube furnace, 750 DEG C under argon protection
Temperature lower calcination 5h, obtains the nickle cobalt lithium manganate of tungsten disulfide fixation.
The nickle cobalt lithium manganate that tungsten disulfide fixation is obtained to the present embodiment is tested, and finds the nickel that the tungsten disulfide is fixed
The average thickness of cobalt manganic acid lithium is 26nm, and the nickle cobalt lithium manganate of the tungsten disulfide by layer structure and spherical structure is with interlayer side
Formula stacking is composited, and the nickle cobalt lithium manganate of the spherical structure is piled up with the pattern of Rotating fields in the template of tungsten disulfide.
The nickle cobalt lithium manganate that the present embodiment is obtained molybdenum bisuphide fixation makes knob as the positive electrode of lithium ion battery
Fastening lithium ionic cell, in the lithium ion battery lithium ion battery, under 0.1C multiplying powers, specific discharge capacity is 235 mAh/g, 10C
Under multiplying power, specific discharge capacity is 215mAh/g.
Embodiment 3
A kind of preparation method of the nickle cobalt lithium manganate that stannic disulfide is fixed is present embodiments provided, which comprises the following steps：
Step one：1mol citric acid nickel, 1mol citric acids cobalt and 1mol manganese citrates are dissolved in 50ml deionized waters, fully
Stirring, is subsequently adding 1mol stannic disulfides as template, stirs 60min, obtain suspension；
Step 2：3mol Quilonorm (SKB) is weighed, is sufficiently stirred for being dissolved in 100ml deionized waters, is obtained lithium acetate solution；
Step 3：Lithium acetate solution is added drop-wise in above-mentioned suspension with the speed of 20m1/min, is stirred in Deca, its stirring
Speed is stirred at room temperature 2. 5h again for 3500rpm, then sucking filtration, and at 100 DEG C is vacuum dried 10h, obtains powder；
Step 4：15min will be ground in the powder dry environment, it is subsequently placed in tube furnace, 750 DEG C under argon protection
Temperature lower calcination 5h, obtains the nickle cobalt lithium manganate of stannic disulfide fixation.
The nickle cobalt lithium manganate that stannic disulfide fixation is obtained to the present embodiment is tested, and finds the nickel that the stannic disulfide is fixed
The average thickness of cobalt manganic acid lithium is 25nm, and the nickle cobalt lithium manganate of the stannic disulfide by layer structure and spherical structure is with interlayer side
Formula stacking is composited, and the nickle cobalt lithium manganate of the spherical structure is piled up with the pattern of Rotating fields in the template of stannic disulfide.
The nickle cobalt lithium manganate that the present embodiment prepared molybdenum bisuphide is fixed is made as the positive electrode of lithium ion battery dynamic
Power battery, this capacity reach more than 195mAh/g, normal temperature circulation life-span 2000 times, 10C discharge and recharges more than 90%.
Embodiment 4
A kind of preparation method of the nickle cobalt lithium manganate that Graphene is fixed is present embodiments provided, which comprises the following steps：
Step one：1mol nickel acetates, 1mol cobaltous sulfates and 1mol manganese sulfates are dissolved in 50ml deionized waters, are sufficiently stirred for,
1mol Graphenes are subsequently adding as template, 60min are stirred, is obtained suspension；
Step 2：3mol Quilonorm (SKB) is weighed, is sufficiently stirred for being dissolved in 100ml deionized waters, is obtained lithium acetate solution；
Step 3：Lithium acetate solution is added drop-wise in above-mentioned suspension with the speed of 20m1/min, is stirred in Deca, its stirring
Speed is stirred at room temperature 2. 5h again for 4000rpm, then sucking filtration, and at 100 DEG C is vacuum dried 15h, obtains powder；
Step 4：15min will be ground in the powder dry environment, it is subsequently placed in tube furnace, 700 DEG C under argon protection
Temperature lower calcination 6h, obtains the nickle cobalt lithium manganate of Graphene fixation.
The nickle cobalt lithium manganate that Graphene fixation is obtained to the present embodiment is tested, and finds the nickel cobalt manganese that the Graphene is fixed
The average thickness of sour lithium is 15nm, and the Graphene by layer structure stacked in interlayer mode with the nickle cobalt lithium manganate of spherical structure
It is composited, the nickle cobalt lithium manganate of the spherical structure is piled up with the pattern of Rotating fields in the template of Graphene.
The nickle cobalt lithium manganate that the present embodiment is obtained Graphene fixation makes power as the positive electrode of lithium ion battery
Battery, remains to keep form during 192 DEG C of high temperature, improves the security performance of battery.
Embodiment 5
A kind of preparation method of the nickle cobalt lithium manganate that molybdenum bisuphide is fixed is present embodiments provided, which comprises the following steps：
Step one：1mol citric acid nickel, 1mol cobaltous chlorides and 1mol manganese chlorides are dissolved in 50ml deionized waters, are fully stirred
Mix, 1mol molybdenum bisuphide is subsequently adding as template, stirs 60min, obtain suspension；
Step 2：3mol Quilonorm (SKB) is weighed, is sufficiently stirred for being dissolved in 100ml deionized waters, is obtained lithium acetate solution；
Step 3：Lithium acetate solution is added drop-wise in above-mentioned suspension with the speed of 20m1/min, is stirred in Deca, its stirring
Speed is stirred at room temperature 2. 5h again for 5000rpm, then sucking filtration, and at 100 DEG C is vacuum dried 12h, obtains powder；
Step 4：15min will be ground in the powder dry environment, it is subsequently placed in tube furnace, 800 DEG C under argon protection
Temperature lower calcination 4h, obtains the nickle cobalt lithium manganate of molybdenum bisuphide fixation.
The nickle cobalt lithium manganate that molybdenum bisuphide fixation is obtained to the present embodiment is tested, and finds the nickel that the molybdenum bisuphide is fixed
The average thickness of cobalt manganic acid lithium is 22nm, and the nickle cobalt lithium manganate of the molybdenum bisuphide by layer structure and spherical structure is with interlayer side
Formula stacking is composited, and the nickle cobalt lithium manganate of the spherical structure is piled up with the pattern of Rotating fields in the template of molybdenum bisuphide.
Embodiment 6
A kind of preparation method of the nickle cobalt lithium manganate that molybdenum bisuphide is fixed is present embodiments provided, which comprises the following steps：
Step one：1mol nickel acetates, 1mol citric acids cobalt and 1mol manganese citrates are dissolved in 50ml deionized waters, are fully stirred
Mix, 1mol molybdenum bisuphide is subsequently adding as template, stirs 60min, obtain suspension；
Step 2：3mol lithium carbonate is weighed, is sufficiently stirred for being dissolved in 100ml deionized waters, is obtained Lithium carbonate solution；
Step 3：Lithium carbonate solution is added drop-wise in above-mentioned suspension with the speed of 20m1/min, is stirred in Deca, its stirring
Speed is 4500rpm, then 2. 5h are stirred at room temperature, then sucking filtration, and at 100 DEG C is vacuum dried 16h, obtains powder；
Step 4：15min will be ground in the powder dry environment, it is subsequently placed in tube furnace, 700 DEG C under argon protection
Temperature lower calcination 6h, obtains the nickle cobalt lithium manganate of molybdenum bisuphide fixation.
The nickle cobalt lithium manganate that molybdenum bisuphide fixation is obtained to the present embodiment is tested, and finds the nickel that the molybdenum bisuphide is fixed
The average thickness of cobalt manganic acid lithium is 28nm, and the nickle cobalt lithium manganate of the molybdenum bisuphide by layer structure and spherical structure is with interlayer side
Formula stacking is composited, and the nickle cobalt lithium manganate of the spherical structure is piled up with the pattern of Rotating fields in the template of molybdenum bisuphide.
Claims (8)
1. the nickle cobalt lithium manganate that a kind of two-dimension nano materials are fixed, it is characterised in that：The nickel cobalt that the two-dimension nano materials are fixed
LiMn2O4 is to be stacked to be composited by two-dimension nano materials with the nickle cobalt lithium manganate of spherical structure in interlayer mode, the spherical junctions
The nickle cobalt lithium manganate of structure is piled up with the pattern of Rotating fields in the template of two-dimension nano materials.
2. the nickle cobalt lithium manganate that two-dimension nano materials according to claim 1 are fixed, it is characterised in that：The two-dimensional nano
Material includes any one in tungsten disulfide, molybdenum bisuphide, stannic disulfide, silene.
3. the nickle cobalt lithium manganate that two-dimension nano materials according to claim 1 are fixed, it is characterised in that：The two-dimensional nano
The thickness of the nickle cobalt lithium manganate that material is fixed is 10nm-35nm.
4. claim requires the preparation method of the nickle cobalt lithium manganate that the two-dimension nano materials described in any one of 1-3 are fixed, its bag
Include following steps：
Step one：Nickel salt, cobalt salt and manganese salt are dissolved in deionized water with the stoichiometric proportion of nickle cobalt lithium manganate, be subsequently adding
Two-dimension nano materials mix as template, obtain suspension；
Step 2：Lithium salts is weighed by the mol ratio of lithium in the nickle cobalt lithium manganate, dissolving in deionized water, obtains lithium salts molten
Liquid；
Step 3：The lithium salt solution is added drop-wise in the suspension, is stirred in Deca, its mixing speed is 2500-
5000rpm, then sucking filtration, and 10h-16h is vacuum dried at 80 DEG C -100 DEG C, obtain powder；
Step 4：By the powder mull, it is subsequently placed in shielding gas in 700 DEG C of -800 DEG C of temperature lower calcination 4h-6h, obtains two
The nickle cobalt lithium manganate that dimension nano material is fixed；
Wherein, the two-dimension nano materials with the mol ratio of lithium salts are（1-5）：1.
5. preparation method according to claim 4, it is characterised in that：In the nickel salt, cobalt salt, manganese salt and lithium salts, extremely
Rare one kind is nitrate or acetate.
6. the preparation method according to claim 4 or 5, it is characterised in that：The nickel salt includes nickel sulfate, nickel nitrate, second
The combination of one or more in sour nickel, citric acid nickel, nickel sulfamic acid and nickel halogenide；The cobalt salt includes cobaltous sulfate, acetic acid
Cobalt, the combination of one or more in cobalt nitrate, citric acid cobalt, halogenation cobalt；The manganese salt includes manganese sulfate, manganese acetate, nitric acid
The combination of one or more in manganese, manganese citrate and manganese halide；The lithium salts includes lithium carbonate, lithium sulfate, lithium nitrate, acetic acid
The combination of one or more in lithium, Lithium Citrate de and lithium halide.
7. preparation method according to claim 4, it is characterised in that：In the suspension, nickel salt, cobalt salt and manganese salt is total
Mass concentration is 50 g/L -70g/L, and in the lithium salt solution, the mass concentration of lithium salts is 5 g/L -10g/L.
8. a kind of lithium ion battery, it is characterised in that：The lithium ion battery is using the two dimension described in any one of claim 1-3
The nickle cobalt lithium manganate that nano material is fixed is used as positive electrode.
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| CN108428872A (en) * | 2018-03-23 | 2018-08-21 | 陈红梅 | A kind of nickelic ternary electrode material of lithium battery and preparation method |
| WO2022205831A1 (en) * | 2021-03-31 | 2022-10-06 | 万向一二三股份公司 | Doped modified positive electrode material with high ion channel stability |
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| CN104701490A (en) * | 2015-04-02 | 2015-06-10 | 北京师范大学 | Preparing method and application of sandwich-structure graphene-based carbon cladding metal oxide |
| CN105140493A (en) * | 2015-10-14 | 2015-12-09 | 广东天劲新能源科技股份有限公司 | Nickel cobalt lithium manganate/graphene/carbon nano tube composite cathode materials and preparation method thereof |
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| CN103440997A (en) * | 2013-08-26 | 2013-12-11 | 中国科学技术大学 | Metal double-hydroxide/molybdenum disulfide nano-composite material and preparation method and application thereof |
| CN104701490A (en) * | 2015-04-02 | 2015-06-10 | 北京师范大学 | Preparing method and application of sandwich-structure graphene-based carbon cladding metal oxide |
| CN105140493A (en) * | 2015-10-14 | 2015-12-09 | 广东天劲新能源科技股份有限公司 | Nickel cobalt lithium manganate/graphene/carbon nano tube composite cathode materials and preparation method thereof |
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| CN108428872A (en) * | 2018-03-23 | 2018-08-21 | 陈红梅 | A kind of nickelic ternary electrode material of lithium battery and preparation method |
| WO2022205831A1 (en) * | 2021-03-31 | 2022-10-06 | 万向一二三股份公司 | Doped modified positive electrode material with high ion channel stability |
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