CN110380041A - A kind of preparation method and application of lithium ion battery hierarchical structure positive electrode - Google Patents
A kind of preparation method and application of lithium ion battery hierarchical structure positive electrode Download PDFInfo
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Abstract
The invention belongs to technical field of lithium ion, and in particular to a kind of lithium ion battery hierarchical structure positive electrode and preparation method thereof, which is specially LiNixCoyAl1‑x‑yOzCl2‑z；0.1≤x≤0.9,0.1≤y≤0.9,1.5≤z≤1.95, it is made through water mixing, fused salt mixing, sintering, crushing, the O element in original NCA material is replaced by adding Cl element, is formed with the class NCA type anode different from traditional NCA material, which has both high potential while having regular uniform microscopic appearance, high-energy-density, high magnification export three kinds of characteristics.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of lithium ion battery hierarchical structure positive electrode
And preparation method and application.
Background technique
Lithium ion battery is the latest generation rechargeable battery after nickel-metal hydride battery.Lithium ion battery is with its embedding lithium voltage
The advantages that height, specific energy height, memory-less effect, small, nontoxic self discharge, become the battery system being widely used at present, and in height
It can gain universal acceptance on portable electronic device.The positive electrode of lithium ion battery is one of core of lithium ion battery.Just
Pole material provides the lithium ion of a large amount of free deintercalations, for improving the work of lithium ion battery in lithium ion battery charging work
It is most important to make the chemical properties such as voltage, specific energy, cycle life.
The positive electrode of existing energy-density lithium ion battery is ternary material.Ni improves material capacity, excessive shadow
Ring cyclicity；Co reduces cationic mixing, stable laminated structure；Mn reduces cost, improves safety and stability；Al improves brilliant
Lattice structure improves cyclicity.By adjusting the ratio of Ni, Co, Mn, Al, the ternary material of different performance is prepared.It is divided into NCM
With two kinds of NCA, be substantially provided to solve cobalt acid lithium (LiCoO2) or lithium nickelate (LiNiO2) stability of layer structure asks
Topic.NCA class anode has the advantage of height ratio capacity, but NCA class material circulation performance is poor, multiplying power discharging low efficiency, and tradition side
Method preparation is complicated, and preparation efficiency is low, Xiang Buchun.
In order to overcome existing technical problem, in existing technology, patent 201410720895.6 proposes lithium-ion electric
The method of modifying of pond positive electrode NCA, but microscopic appearance is reunited seriously, and size is larger, is unfavorable for capacity release, and preparation side
Formula is complicated.
Patent 201510878319.9 proposes a kind of preparation side for improving lithium ion battery NCA positive electrode compacted density
Method, but fused-salt medium method proposed in claim be NCA preparation after ex situ physical mixed, interfacial contact impedance compared with
Greatly, from pattern and microscopic appearance irregular contact is more.
Patent 201510175555.4 proposes lithium ion battery LiNi1-x-yCoxAlyO2The preparation method of material, but patent
Data show that the material granule degree of this method preparation is big, and pattern is reunited seriously, and structure is irregular, the discharge performance under 2C multiplying power
Decay extremely serious.
Patent CN201610741604.0, which is disclosed, is added calcining preparation jointly in nickel cobalt aluminium co-precipitation presoma for LiCl
The method of NCA tertiary cathode material, and obtained NCA tertiary cathode material reversible specific capacity is 148mAh/g, and capacity is kept
Rate is 85%, due to not after the presoma stage is added LiCl but is added to molding NCA presoma as lithium salts
Calcining, cannot play the modification advantage of LiCl, finally obtained product remains LiNixCoyAlzO2(x+y+z=1), Cl element
It is lost after high temperature sintering, does not replace O element, so discharge performance is still undesirable.
In short, can quickly prepare without a kind of effective method with good big high rate performance in the prior art
NCA class positive electrode, existing NCA class positive electrode are difficult to have both high potential, high-energy-density, and high magnification exports three kinds of characteristics, no
Meet the power demands of modern advanced electronics.
Summary of the invention
The present invention is in order to solve the above technical problems, provide a kind of lithium ion battery hierarchical structure positive electrode and preparation
Methods and applications.
It is realized particular by following technical scheme:
A kind of lithium ion battery hierarchical structure positive electrode, the hierarchical structure positive electrode chemical formula are specially
LiNixCoyAl1-x-yOzCl2-z；0.1≤x≤0.9,0.1≤y≤0.9,1.5≤z≤1.95；The hierarchical structure positive electrode
Microscopic appearance includes primary structure and secondary structure；The primary structure is layer structure, and secondary structure is chondritic；It is described
Layer structure is nanometer sheet；Chondritic is micron ball.
The microscopic appearance is at least to stack the micron ball constituted by 10 individual layer nanometer sheets.
The thickness in monolayer of the nanometer sheet is in 30nm~180nm.
It is a further object of the present invention to provide the lithium ion battery preparation method of hierarchical structure positive electrode, packets
Include following steps:
(1) water mixes: taking lithium salts, nickel salt, cobalt salt, aluminium salt is placed in blender, adds water and stirs to solution and clarify, obtain water-soluble
Liquid is spare；
(2) fused salt mixes: LiCl being 1. heated to molten state, obtains supernatant liquid A；2. step (1) is obtained water-soluble
Liquid is placed in the heating 2h~for 24 hours of the air dry oven within the scope of 80 DEG C~180 DEG C, obtains melt liquid B, and taking-up is placed on dry environment
In it is spare；3. by supernatant liquid A inject melt liquid B in, then be placed at 160 DEG C~200 DEG C in air dry oven heat 1h~
4h obtains presoma melt liquid C；
(3) it is sintered: the obtained presoma melt liquid C in step (2) being put into sintering furnace, is risen in aerobic environment
Temperature obtains hierarchical structure positive electrode solid after cooling to 750 DEG C~950 DEG C, isothermal holding 8h~16h；
(4) it crushes: the obtained hierarchical structure positive electrode solid in step (4) is crushed, be sieved, be classified
Structure positive electrode.
In the step (1), the lithium salts is lithium nitrate；The nickel salt is nickel nitrate, any one in six water nickel nitrates
Or several composition；The cobalt salt is cobalt nitrate, any one or the combination of several of them object in cobalt nitrate hexahydrate；The aluminium salt is
Any one or the combination of several of them object in aluminum nitrate, nine water aluminum nitrates.
In the step (2), the water and lithium salts, nickel salt, cobalt salt, aluminium salt mixture quality ratio are 3~10:1.
In the step (2), the water is deionized water, distilled water, any one in ultrapure water.
In the step (2), the speed of agitator is 80r/min~600r/min.
In the step (3), the LiCl heating temperature is 620 DEG C~700 DEG C.
In the step (3), the dry environment is humidity≤3%.
In the step (5), the pulverizer revolving speed is 5000r/min~6000r/min, and grinding time is 1~3min.
The hierarchical structure positive electrode is powder, granularity >=200 mesh.
It is a further object of the present invention to provide application of the hierarchical structure positive electrode in lithium ion battery.
The utility model has the advantages that
The first, electric conductivity is improved.The O element in original NCA material is replaced by adding Cl element, is formed with different from biography
The class NCA type anode of system NCA material, improves Li by the congenital powerful ionic conductivity of LiCl bring+Insertion and abjection
Dynamics, the i.e. Li of O-Li-O middle layer+Deintercalation not will receive the obstruction of electron exchange, because of Cl-Compare O2-It is easier to lose
Electronics.Therefore, Li when high-multiplying power discharge+The degree of deintercalation will be accelerated, to reduce impedance, weaken polarization phenomena.Thus improve
The monolithic conductive performance of NCA class material, and O element is replaced by Cl element, cause Ni that Ni is presented2+And Ni3+Form coexist in
In hierarchical structure positive electrode, and with the increase of Cl element doping amount, Ni2+Accounting can also be incremented by, lead to performance degradation, because
And the doping of Cl is defined in the present invention, to reduce cationic mixing.The second, hierarchical structure is constructed, specific energy is improved, it is high
Multiplying power output.The present invention proposes that doping method is blended in a kind of fused salt, and compared with direct water hybrid mode, fused salt proposed by the present invention is total
It is mixed that all precursor materials can be enabled to realize that atom uniformly mixes in the molten state, and dividing for mass can be obtained by sintering
Level structure positive electrode LiNixCoyAl1-x-yOzCl2-z, the positive electrode that possesses hierarchical structure have both layer structure and chondritic
Double dominant.Third, with regular microscopic appearance.It can be seen that positive electrode has apparent classification according to scanning electron microscope (SEM) photograph
Structure, hierarchical structure size are uniform, regular；Under the scanning electron microscope of low range, equally distributed chondritic is presented, with
The chondritic of reunion is compared, and chondritic of the invention increases specific surface area, to obtain more active sites and electricity
Matter contact is solved, specific energy is improved；Meanwhile under high magnification, the nanometer laminated structure of plane extreme length >=1 μm is easy to electronics
It is removed on the contact interface of positive electrode and electrolyte, improves multiplying power and cyclicity.
To sum up, hierarchical structure positive electrode prepared by the present invention also possesses while with regular uniform microscopic appearance
The high potential of NCA itself, height ratio capacity, and capacity of the NCA material under high magnification has been greatly optimized by above-mentioned enhancing principle
Output, so that hierarchical structure class NCA anode provided by the invention has both high potential, height ratio capacity, high magnification exports three kinds of characteristics.
In addition, strict control water of the present invention and lithium salts, nickel salt, cobalt salt, aluminium salt water-solid ratio, improve mixing efficiency, together
When in turn avoid the too long problem of dewatering time；Strict control water and lithium salts, nickel salt, cobalt salt, aluminium salt mixing speed, stirring speed
Degree consolidates mass ratio and stirring amount of substance according to water to determine, so that material mixing is abundant and centrifugal phenomenon, Jin Ergai will not occur
It has been apt to the dispersibility of material, has reduced mixing energy consumption；Strict control lithium chloride heating temperature, on the one hand, heating temperature is according to chlorine
Change lithium quality to determine, to ensure material melts efficiency, reduces melting energy consumption, on the other hand, heating temperature is also according to molten liquid
Body B mass determines, to ensure that lithium chloride can be quenched to 180 DEG C of snowflake sheet solid-states below from 620 DEG C or more of liquid
When (quickly solidify elongations because of thermal stress driving), the reaction of enough heat acceleration moleculars can be discharged by itself quenching and is moved
Mechanics enables it quickly diffuse in melt liquid B；Strict control heating temperature, if heating temperature is excessively high, while energy consumption increases
Also it easily enables the presoma of chloride containing lithium generate accumulation of reuniting, is unfavorable for nanometer sheet ordered stacks in hierarchical structure, and heating time
Temperature is too low, is unfavorable for lithium chloride and melt liquid B progress is uniformly atom doped, local element ratio is unbalance, molecule microcell
Product is inconsistent, is easy to produce distortion of lattice, in addition, because the temperature that lithium chloride sloughs 1/2 crystallization water is 160 DEG C, so this
Invention selects this temperature as minimum heating temperature；The humidity of strict control dry environment ensures the moisture content of presoma, so that
It is dehydrated less in sintering process, and then improves moisture abjection rate, abjection amount and energy consumption in sintering process, so as to improve just
The space structure of pole material is unfavorable for the generation of layer structure if presoma moisture content is high, because will cause material surface when dehydration
It forms porous structure rather than regular layered appearance, can not also form nanometer sheet and carry out stacking in smooth layered planes and form ball
Shape structure；Strict control pulverizer revolving speed is conducive to ensure powder efficient pulverizing and avoids the destruction to microscopic appearance；Stringent control
The granularity of positive electrode processed is conducive to prepare electrode.
The present invention by lithium chloride be melt into supernatant liquid A injection containing lithium salts, nickel salt, cobalt salt, aluminium salt melt liquid B
In, so that layer structure occurs accumulation and forms chondritic, and the heating temperature of strict control presoma melt liquid C is 160
DEG C~200 DEG C, it is ensured that synthesis rate effectively controls ion diffusion and atom doped, guarantee laminar nano piece crystallization, and certainly
Main dress stacking forms micron ball.It is atom doped non-uniform while can not also slough LiCl1/2H if temperature is too low2In O
1/2 crystallization water, is also easy to produce distortion of lattice, if temperature crosses high energy consumption and increases and directly reunite, is unable to the micron ball of formation rule.
Detailed description of the invention
Fig. 1 is the XRD test chart of hierarchical structure positive electrode made from the embodiment of the present invention one；
Fig. 2 is the SEM test chart of hierarchical structure positive electrode made from the embodiment of the present invention one；
Fig. 3 is the SEM test chart of hierarchical structure positive electrode made from the embodiment of the present invention two；
Fig. 4 is the SEM test chart of hierarchical structure positive electrode made from the embodiment of the present invention three；
Fig. 5 is the SEM test chart of hierarchical structure positive electrode made from the embodiment of the present invention four；
Fig. 6 is the EDS test chart of hierarchical structure positive electrode made from the embodiment of the present invention four
Fig. 7 is discharge curve comparison diagram of the lithium ion battery under 1C multiplying power made from four kinds of embodiments of the invention；
Fig. 8 is discharge curve comparison diagram of the lithium ion battery under 10C multiplying power made from four kinds of embodiments of the invention.
Specific embodiment
Specific embodiments of the present invention will be described in further detail below, but the invention is not limited to these realities
Mode is applied, it is claimed to still fall within the claims in the present invention for any improvement or replacement on the present embodiment essence spirit
Range.
Embodiment 1
A kind of lithium ion battery hierarchical structure positive electrode, chemical formula is specially LiNi0.8Co0.19Al0.01O1.90Cl0.1；
The microscopic appearance is at least to stack the micron ball constituted by 10 individual layer nanometer sheets, preparation method specifically includes the following steps:
1. weighing: weighing lithium nitrate, nickel nitrate, cobalt nitrate, aluminum nitrate and chlorination according to stoichiometric ratio according to molecular formula
Lithium amounts to 100g；
2. water mixes: by step 1. in load weighted lithium nitrate, nickel nitrate, cobalt nitrate, aluminum nitrate is added in blender
1000g distilled water is stirred evenly at revolving speed 80r/min, spare to get aqueous solution until obtaining clear solution；
3. fused salt mixes: LiCl being contained in ceramic vessel, supernatant liquid A is heated at 620 DEG C；Again 2. by step
The aqueous solution of acquisition pours into ceramic vessel, and air dry oven heating for 24 hours, obtains melt liquid B under the conditions of being placed in 80 DEG C, takes out
It is placed on spare in the dry environment that humidity is 1.2%；Supernatant liquid A is injected in melt liquid B later, places into 160 DEG C
4h is heated in lower air dry oven, obtains presoma melt liquid C；
4. sintering: by step 3. in obtained presoma melt liquid C be put into sintering furnace, heat up in air atmosphere
To 750 DEG C of holding 8h, hierarchical structure positive electrode solid is obtained after cooling；
5. crush: by step 4. in obtained hierarchical structure positive electrode solid be placed in pulverizer with 5000r/min
2min is crushed, 200 meshes is crossed, obtains hierarchical structure positive electrode LiNi0.8Co0.19Al0.01O1.9Cl0.1；
The LiNi that the present embodiment obtains0.8Co0.19Al0.01O1.9Cl0.1The XRD test chart of positive electrode is shown in Fig. 1, SEM test
Figure is shown in Fig. 2.
Embodiment 2
A kind of lithium ion battery hierarchical structure positive electrode, chemical formula are specially
LiNi0.37Co0.6Al0.03O1.95Cl0.05；The microscopic appearance is at least to stack the micron ball constituted by 10 individual layer nanometer sheets,
Preparation method specifically includes the following steps:
1. weighing: weighing lithium nitrate, nickel nitrate, cobalt nitrate, aluminum nitrate and chlorination according to stoichiometric ratio according to molecular formula
Lithium amounts to 500g；
2. water mixes: by step 1. in load weighted lithium nitrate, nickel nitrate, cobalt nitrate, aluminum nitrate is added in blender
3500g ultrapure water is stirred evenly at revolving speed 180r/min, spare to get aqueous solution until obtaining clear solution；
3. fused salt mixes: LiCl being contained in ceramic vessel, supernatant liquid A is heated at 670 DEG C；Again 2. by step
The aqueous solution of acquisition pours into ceramic vessel, and air dry oven heats 10h under the conditions of being placed in 160 DEG C, obtains melt liquid B, takes
It is placed on out spare in the dry environment that humidity is 1.5%；Supernatant liquid A is injected in melt liquid B later, places into 170
2h is heated at DEG C in air dry oven, obtains presoma melt liquid C；
4. sintering: by step 3. in obtained presoma melt liquid C be put into sintering furnace, heat up in oxygen atmosphere
To 800 DEG C of holding 10h, hierarchical structure positive electrode solid is obtained after cooling；
5. crush: by step 4. in obtained hierarchical structure positive electrode solid be placed in pulverizer with 5500r/min
1min is crushed, 250 meshes is crossed, obtains hierarchical structure positive electrode LiNi0.37Co0.6Al0.03O1.95Cl0.05；
The LiNi that the present embodiment obtains0.37Co0.6Al0.03O1.95Cl0.05The SEM test chart of positive electrode is shown in Fig. 3.
Embodiment 3
A kind of lithium ion battery hierarchical structure positive electrode, chemical formula is specially LiNi0.35Co0.6Al0.05O1.9Cl0.1；
The microscopic appearance is at least to stack the micron ball constituted by 10 individual layer nanometer sheets, preparation method specifically includes the following steps:
1. weighing: weighing lithium nitrate, six water nickel nitrates, cobalt nitrate hexahydrate, nine water according to stoichiometric ratio according to molecular formula
Aluminum nitrate and lithium chloride amount to 500g.
2. water mix: by step 1. in load weighted lithium nitrate, six water nickel nitrates, cobalt nitrate, aluminum nitrate is in blender
1500g distilled water is added, is stirred evenly at 200r/min, it is spare to get aqueous solution until obtaining clear solution；
3. fused salt mixes: LiCl being contained in ceramic vessel, supernatant liquid A is heated at 670 DEG C；Again 2. by step
The aqueous solution of acquisition pours into ceramic vessel, and air dry oven heats 12h under the conditions of being placed in 160 DEG C, obtains melt liquid B, takes
It is placed on out spare in the dry environment that humidity is 3%；Supernatant liquid A is injected in melt liquid B later, places into 180 DEG C
1h is heated in lower air dry oven, obtains presoma melt liquid C；
4. sintering: by step 3. in obtained presoma melt liquid C be put into sintering furnace, heat up in air atmosphere
To 850 DEG C of holding 12h, hierarchical structure positive electrode solid is obtained after cooling；
5. crush: by step 4. in obtained hierarchical structure positive electrode solid be placed in pulverizer with 5700r/min
1min is crushed, 300 meshes is crossed, obtains hierarchical structure positive electrode LiNi0.35Co0.6Al0.05O1.9Cl0.1；
The LiNi that the present embodiment obtains0.35Co0.6Al0.05O1.9Cl0.1The SEM test chart of positive electrode is shown in Fig. 4.
Embodiment 4
A kind of lithium ion battery hierarchical structure positive electrode, chemical formula are specially
LiNi0.39Co0.6Al0.01O1.92Cl0.08；The microscopic appearance is at least to stack the micron ball constituted by 10 individual layer nanometer sheets,
Preparation method specifically includes the following steps:
1. weighing: weighing lithium nitrate, six water nickel nitrates, cobalt nitrate hexahydrate, nine water according to stoichiometric ratio according to molecular formula
Aluminum nitrate and lithium chloride amount to 500g；
2. water mixes: by step 1. in load weighted lithium nitrate, six water nickel nitrates, cobalt nitrate, aluminum nitrate is placed in blender
In, 2500g deionized water is added, stirring to solution is clarified at revolving speed 600r/min, and it is spare to obtain aqueous solution；
3. fused salt mixes: LiCl being contained in ceramic vessel, supernatant liquid A is heated at 650 DEG C；Again 2. by step
The aqueous solution of acquisition pours into ceramic vessel, and air dry oven heats 2h under the conditions of being placed in 180 DEG C, obtains melt liquid B, takes out
It is placed on spare in the dry environment that humidity is 0.3%；Supernatant liquid A is injected in melt liquid B later, places into 200 DEG C
1h is heated in lower air dry oven, obtains presoma melt liquid C；
4. sintering: by step 3. in obtained presoma melt liquid C be put into sintering furnace, heat up in air atmosphere
To 950 DEG C of holding 16h, hierarchical structure positive electrode solid is obtained after cooling；
5. crush: by step 4. in obtained hierarchical structure positive electrode solid be placed in pulverizer with 6000r/min
3min is crushed, 300 meshes is crossed, obtains hierarchical structure positive electrode LiNi0.39Co0.6Al0.01O1.92Cl0.08；
The LiNi that the present embodiment obtains0.39Co0.6Al0.01O1.92Cl0.08The SEM test chart of positive electrode is shown in Fig. 5, EDS member
Plain analysis chart is shown in Fig. 6.
Application examples 1
Respectively with embodiment 1, embodiment 2, embodiment 3, hierarchical structure positive electrode and conductive charcoal prepared by embodiment 4
It is black, PVDF bonding agent according to weight percent=9:0.5:0.5 in nmp solvent after mixing, by slurry be coated in aluminium foil
On, dry 12h, the positive plate of Ф 16mm is made of mold at 100 DEG C；CR2032 button is prepared into inert-atmosphere glove box
Formula battery, battery cathode are lithium piece, with 1M LiPF6Electrolyte (volume ratio 1:1) is collectively constituted with EC/DEC；Under 1C multiplying power
It discharges, is calculated by blanking voltage of 3.0V, one specific capacity of embodiment is 176.33mAh/g, and two specific capacity of embodiment is
173.33mAh/g, three specific capacity of embodiment are 165.62mAh/g, and example IV specific capacity is 157.98mAh/g.Discharge performance
Fig. 7 is shown in comparison.
Application examples 2
Respectively with embodiment one, embodiment two, embodiment three, the hierarchical structure positive electrode and conduction of example IV preparation
Carbon black, PVDF bonding agent according to weight percent=9:0.5:0.5 in nmp solvent after mixing, by slurry be coated in aluminium
On foil, dry 12h, the positive plate of Ф 16mm is made of mold at 100 DEG C；CR2032 is prepared into inert-atmosphere glove box
Button cell, battery cathode are lithium piece, with 1M LiPF6Electrolyte (volume ratio 1:1) is collectively constituted with EC/DEC；In 10C multiplying power
Under discharge, calculated by blanking voltage of 3.0V, one specific capacity of embodiment is 116.95mAh/g, and two specific capacity of embodiment is
121.16mAh/g, three specific capacity of embodiment are 121.56mAh/g, and example IV specific capacity is 119.44mAh/g.Discharge performance
Fig. 8 is shown in comparison.
Claims (10)
1. a kind of lithium ion battery hierarchical structure positive electrode, it is characterised in that: the hierarchical structure positive electrode chemical formula
Specially LiNixCoyAl1-x-yOzCl2-z；0.1≤x≤0.9,0.1≤y≤0.9,1.5≤z≤1.95；Hierarchical structure anode
The microscopic appearance of material includes primary structure and secondary structure；The primary structure is layer structure, and secondary structure is spherical knot
Structure；Layered structure is nanometer sheet；Chondritic is micron ball.
2. a kind of lithium ion battery hierarchical structure positive electrode according to claim 1, it is characterised in that: described microcosmic
Pattern is at least to stack the micron ball constituted by 10 individual layer nanometer sheets.
3. a kind of lithium ion battery hierarchical structure positive electrode according to claim 1, it is characterised in that: the nanometer
The thickness in monolayer of piece is in 30nm~180nm.
4. the preparation method of a kind of lithium ion battery hierarchical structure positive electrode according to claim 1, including water mixing,
Fused salt mixing, sintering, pulverising step, it is characterised in that: the step of fused salt mixes are as follows:
1. LiCl is heated to molten state, supernatant liquid A is obtained；
2. water mixing step gains are placed in the heating 2h~for 24 hours of the air dry oven within the scope of 80 DEG C~180 DEG C, molten liquid is obtained
Body B, taking-up are placed on spare in dry environment；
3. supernatant liquid A is injected in melt liquid B, then heating 1h~4h in air dry oven is placed at 160 DEG C~200 DEG C,
Obtain presoma melt liquid C.
5. the lithium ion battery according to claim 4 preparation method of hierarchical structure positive electrode, it is characterised in that: institute
State fused salt mixing step 1. in, the heating temperature of LiCl is 620 DEG C~700 DEG C.
6. the lithium ion battery according to claim 4 preparation method of hierarchical structure positive electrode, it is characterised in that: institute
State fused salt mixing step 3. in, humidity≤3% of the dry environment.
7. the preparation method of hierarchical structure positive electrode according to claim 4, it is characterised in that: the water mixing step
Gains are that consolidate mass ratio by water with lithium salts, nickel salt, cobalt salt, aluminium salt be that 3~10:1 is stirred to water.
8. the preparation method of hierarchical structure positive electrode according to claim 4, it is characterised in that: the water mixing step
The revolving speed of the stirring of gains is 80r/min~600r/min.
9. the preparation method of hierarchical structure positive electrode according to claim 4, it is characterised in that: the lithium salts is nitric acid
Lithium；The nickel salt is nickel nitrate, any one or the combination of several of them object in six water nickel nitrates；The cobalt salt is cobalt nitrate, six water
Any one or the combination of several of them object in cobalt nitrate；The aluminium salt is aluminum nitrate, any one or a few in nine water aluminum nitrates
Composition.
10. lithium ion battery according to claim 1-3 is with hierarchical structure positive electrode in lithium ion battery
Application.
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