CN109950530A - With the nickelic tertiary cathode material and preparation method thereof for improving electrical property - Google Patents
With the nickelic tertiary cathode material and preparation method thereof for improving electrical property Download PDFInfo
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Abstract
The present invention relates to having the nickelic tertiary cathode material and preparation method thereof for improving electrical property, the positive electrode is obtained by positive electrode matrix through overpickling and cladding, and the positive electrode matrix is by formula Li (Ni1‑x‑yCoxMny)O2It indicates, wherein 0,0.4 > y > 0 of 1-x-y >=0.5,0.4 > x >；The preparation method includes that positive electrode matrix is added in scattered acid solution to carry out pickling, removes dispersing agent, and calcining obtains washing rear positive electrode；It is added in the dispersion liquid containing silane coupling agent, solvent evaporated, is dried in vacuo under different temperatures to get modified tertiary cathode material is arrived rear positive electrode is washed again.The discharge performance for the nickelic tertiary cathode material that the present invention is prepared is good, preparation method of the invention improves water resistance, thermal stability and the mechanical property of material, improve the high rate performance of material, this preparation method condition is simple, controllable, it is low to the device requirement of production, it is the Practical Approach that can be promoted the use of.
Description
Technical field
The present invention relates to cell positive material field, in particular to there is the height for improving electrical property in a kind of lithium ion battery
Nickel positive electrode and preparation method thereof.
Background technique
The high defect of nickelic positive electrode surface residual alkali content not only to its storage and using when ambient humidity mention
Requirements at the higher level are gone out, while also having caused cell positive material Stability of Slurry poor, has been easy to appear viscosity and increases even generation fruit
Freeze phenomenon, causes the paintability in battery pole piece manufacturing process poor.Nickelic positive electrode surface residual alkali content is higher also
Will lead to battery capacity it is low, produce gas expansion, cause battery safety to reduce.The poor cyclicity of nickelic tertiary cathode material
The popularization of material large area can be limit always with security performance, for these problems, be used many measures to improve
The chemical property of ternary material, such as ion doping, surface cladding, and using electrolysis additive etc., but no matter which kind of method
Means are all very single, and improved effect is difficult to persistently, such as alumina-coated can effectively improve material interface stability, and
The cycle performance of material can be promoted, however, the aluminium oxide at material interface can be reacted with the HF in electrolyte, this is also oxidation
Aluminium covering material not can be carried out the reason of longer time protection.Li(Ni0.8Co0.1Mn0.1)O2Middle nickel content is relatively high, material
PH value is also very high, and water imbibition is very strong, understands the moisture absorption in transport of materials and with slurry process, causes battery performance sharply to decline, in material
Difficulty is caused in terms of storage and industrialization.
Therefore, the electrical property that a kind of method for improving nickelic tertiary cathode material electrical property makes nickelic positive electrode is needed
Good, method is simple, meets the needs of industrialization production.
Summary of the invention
To solve the above-mentioned problems, present inventor has performed sharp studies, as a result, it has been found that: nickelic positive electrode matrix is first
It with Bronsted acid pickling, then calcines, is then coated again with silane coupling agent to rear nickelic positive electrode is washed, to be had
It is improved the nickelic tertiary cathode material of electrical property.The good rate capability for the nickelic positive electrode that the present invention is prepared, electric discharge
Performance is good, good cycle.This preparation method condition is simple, low to the device requirement of production, thereby completing the present invention.
The purpose of the present invention is to provide following aspect:
(1) there is the nickelic tertiary cathode material for improving electrical property, the positive electrode is by positive electrode matrix through peracid
It washes and coats, positive electrode matrix is by formula Li (Ni1-x-yCoxMny)O2It indicates, wherein 1-x-y >=0.5,0.4 > x >
0,0.4 > y > 0, it is preferable that positive electrode matrix is Li (Ni0.8Co0.1Mn0.1)O2。
(2) a kind of preparation method with the nickelic tertiary cathode material for improving electrical property, comprising the following steps:
Step 1, positive electrode matrix is added in Bronsted acid dispersion liquid, is stirred, remove dispersing agent；
Step 2, the system that step 1 obtains is calcined, obtains washing rear positive electrode；
Step 3, rear positive electrode will be washed to mix with covering, and will post-process, obtains final products.
(3) nickelic tertiary cathode material made from the method according to above-mentioned (2),
The battery of the positive electrode preparation is within the scope of 3.0V~4.3V with 1C rate charge-discharge, initial discharge specific capacity
Up to 177mAh/g or more；And/or
The battery of positive electrode preparation within the scope of 3.0V~4.3V with after 1C circulation 200 times, coulombic efficiency
It is 85% or more.
What is provided according to the present invention has the nickelic tertiary cathode material and preparation method thereof for improving electrical property, has following
The utility model has the advantages that
1) battery of nickelic tertiary cathode material preparation provided by the invention is filled within the scope of 3.0V~4.3V with 1C multiplying power
Electric discharge, initial discharge specific capacity reach 177mAh/g or more；And/or
The battery of positive electrode preparation within the scope of 3.0V~4.3V with after 1C circulation 200 times, coulombic efficiency
It is 85% or more；
2) washing calcining is carried out to positive electrode matrix using Bronsted acid in method provided by the invention, it is environmental-friendly, just
In operation processing；It effectively reduces remaining alkali content, and can guarantee electrical property without being substantially reduced, but also in ternary material table
Face forms one layer of lithium phosphate clad, improves the percent of pass of lithium ion deintercalation；
3) covering is added after the calcining of proton acid elution, the water resistance and mechanical property of ternary material not only can be improved
Can, and can isolate contact of the positive electrode with electrolyte, reduce side reaction and extend the material circulation service life, improve it is nickelic just
The electrical property of pole material；
4) entire preparation method simple process, the solvent used is cheap, of less demanding to the production equipment used,
It while easily operated, reduces costs, these factors are conducive to the popularization of industrialization.
Detailed description of the invention
Fig. 1 shows original material NCM811 in original material NCM811 and 6~comparative example of comparative example 8 and directly coats kh560
SEM figure；
Fig. 2 shows original material NCM811 in 1~embodiment of embodiment 3 coated after phosphoric acid is washed kh560 SEM figure；
Fig. 3 shows original material NCM811 in original material NCM811 and 6~comparative example of comparative example 8 and directly coats kh560
XRD diagram；
Fig. 4 shows original material NCM811 and original material NCM811 in 1~embodiment of embodiment 3 and washes Hou Bao through phosphoric acid
Cover the XRD diagram of kh560；
Fig. 5 shows original material NCM811 in original material NCM811 and 6~comparative example of comparative example 8 and directly coats kh560
High rate performance curve graph；
Fig. 6 shows original material NCM811 and original material NCM811 in 1~embodiment of embodiment 3 and washes Hou Bao through phosphoric acid
Cover the high rate performance curve graph of kh560；
Fig. 7 shows original material NCM811 in original material NCM811 and 6~comparative example of comparative example 8 and directly coats kh560
Cycle performance curve graph；
Fig. 8 shows original material NCM811 and original material NCM811 in 1~embodiment of embodiment 3 and washes Hou Bao through phosphoric acid
Cover the cycle performance curve graph of kh560；
Fig. 9 shows original material NCM811 and original material NCM811 in 1~embodiment of embodiment 3 and washes Hou Bao through phosphoric acid
Cover the TEM figure of kh560；
Figure 10 shows the cycle performance curve graph of different Bronsted acid pickling original material NCM811；
Figure 11 shows embodiment 2 and the NCM811 of comparative example 1~2 coats following for kh560 after different Bronsted acid pickling
Ring performance chart；
The cycle performance that Figure 12 shows the different silane coupling agents cladding original material NCM811 of comparative example 7,9 and 10 is bent
Line；
Figure 13 shows embodiment 2 and the different silane coupling agents of comparative example 4~5 coat the NCM811 material after phosphoric acid is washed
Cycle performance curve graph；
Figure 14, which shows the original material NCM811 of embodiment 2 and washes through phosphoric acid, washes Hou Bao through lithium dihydrogen phosphate with comparative example 3
Cover the cycle performance curve graph of kh560；
Figure 15 shows the cycle performance curve graph that original material NCM811 coats kh560 after different amounts of phosphoric acid is washed.
Specific embodiment
Present invention will now be described in detail, and the features and advantages of the invention will become more with these explanations
It is clear, clear.
Dedicated word " exemplary " means " being used as example, embodiment or illustrative " herein.Here as " exemplary "
Illustrated any embodiment should not necessarily be construed as preferred or advantageous over other embodiments.Although each of embodiment is shown in the attached drawings
In terms of kind, but unless otherwise indicated, it is not necessary to attached drawing drawn to scale.
The object of the present invention is to provide having the nickelic tertiary cathode material for improving electrical property, the positive electrode is by anode
Material matrix is obtained through overpickling and cladding, and the positive electrode matrix is by formula Li (Ni1-x-yCoxMny)O2It indicates, wherein 1-
0,0.4 > y > 0 of x-y >=0.5,0.4 > x >；Preferably, the positive electrode matrix is Li (Ni0.8Co0.1Mn0.1) O2。
Another object of the present invention is to provide the preparation method with nickelic three positive electrode for improving electrical property, packet
Include following steps:
Step 1, positive electrode matrix is added in Bronsted acid dispersion liquid, is stirred, remove dispersing agent；
Step 2, the system that step 1 obtains is calcined, obtains washing rear positive electrode；
Step 3, rear positive electrode will be washed to mix with covering, and will post-process, obtains final products.
Step 1, positive electrode matrix is added in Bronsted acid dispersion liquid, is stirred, remove dispersing agent.
In the present invention, the positive electrode matrix is by formula Li (Ni1-x-yCoxMny)O2It indicates, wherein 1-x-y >=0.5,
0.4 > x >, 0,0.4 > y > 0；Further, the positive electrode matrix is Li (Ni0.8Co0.1Mn0.1)O2。
In the present invention, the Bronsted acid is acetic acid, oxalic acid or phosphoric acid, preferably phosphoric acid.
While high-nickel material receives significant attention, the chemical combination image LiOH of the abundant residues lithium on surface and
Li2CO3, these compounds will form Li when battery high voltage is run2O and CO2Gas, these can all reduce battery charging and discharging
Performance can also be such that battery temperature increases, expansion is even exploded.The inventors discovered that in processing high-nickel material surface residual lithium
Compound is, it is preferable to use a kind of Bronsted acid: phosphoric acid can disposably consume 3 Li when with phosphatase reaction+Form Li3PO4,
In addition phosphoric acid is also a kind of good ion conductor (6*10-8S/cm).First by original material Li (Ni0.8Co0.1Mn0.1)O2Use matter
After sub- acid phosphoric acid is washed, the amount for reducing surface residual lithium improves the cycle performance of battery to reduce the high temperature inflatable of battery.
The dosage of the Bronsted acid is that the mass ratio of Bronsted acid and positive electrode matrix is (0.001~1): 100, preferably
For (0.005~0.05): 100, further preferably 0.5:98.5,1:99,1.5:98.5 or 2:98, still more preferably for
1:99。
The inventors discovered that positive electrode surface can be caused to corrode when Bronsted acid dosage is excessively high, serious destruction material
Pattern, to cause the missing of lithium ion inside positive electrode, crystal structure is destroyed, and influences positive electrode electrical property, not only not
The electrical property of ternary material can be improved, will be greatly reduced the electrical property of ternary material instead.When Bronsted acid dosage is too small, and not
Remaining LiOH and Li can be effectively reduced2CO3Amount, thus the electrical property of ternary material cannot be improved, the inventors discovered that, proton
The dosage of acid is preferably that the mass ratio of Bronsted acid and ternary material is 1:99.
The inventors discovered that Bronsted acid is preferably phosphoric acid, after phosphoric acid is washed, ternary material surface just forms Li3PO4Clad,
Li3PO4Clad reduces HF in electrolysis, and, to the solubility of material, recycling under high magnification makes battery maintain preferable stabilization
Property.
In the present invention, the Bronsted acid dispersion liquid is that Bronsted acid is dispersed with dispersing agent, and the dispersing agent is alcohols, preferably
For methanol, ethyl alcohol, isopropanol, more preferably ethyl alcohol, further preferably dehydrated alcohol.The inventors discovered that using dehydrated alcohol
The concentration of Bronsted acid can be effectively reduced in dispersion Bronsted acid, and guarantees that Bronsted acid consumes remaining LiOH and Li2CO3。
In the present invention, the temperature for removing dispersing agent is 70~90 DEG C, and heating evaporation removes dispersing agent at a temperature of this.
In a preferred embodiment, the temperature for removing dispersing agent is 80 DEG C.The mode of dispersing agent is removed without spy
It does not limit, oil bath heating is used in the present invention, atmospheric evaporation falls dispersing agent.
Step 2, the system that step 1 obtains is calcined, obtains washing rear positive electrode.
The calcination temperature is 450-550 DEG C, preferably 500 DEG C；The calcination time is 4-6h, preferably 5h.Herein
The purpose of calcining is that proton acid phosphoric acid can generate one layer of Li with the remaining lithium on surface on the surface of the material3PO4Layer protects bulk material.
Abundant experimental results show Bronsted acid treated that the electrical property decline of positive electrode is unobvious.Not by any reason
By limitation, it is believed that the Bronsted acid that the present invention selects is not easy to make the lattice structure of positive electrode while reaction with however, residual base
At destruction.
Step 3, rear positive electrode will be washed to mix with covering, and will post-process, obtains final products.
The covering is silane coupling agent, preferably kh550, kh560 or kh570, further preferably kh560, institute
The dosage for stating silane coupling agent is silane coupling agent and washes the mass ratio of rear positive electrode as (0.001~1): 100, preferably
(0.005~0.05): 100, further preferably 0.5:99.5,1:99 or 2:98 are still more preferably 1:99.
Kh560 silane coupling agent, γ-glycidyl ether oxygen propyl trimethoxy silicane are a kind of epoxy-functional silane.
Li(Ni0.8Co0.1Mn0.1)O2Middle nickel content is relatively high, and the pH value of material is also very high, and water imbibition is very strong, transports in material
It is defeated and and slurry process can the moisture absorption, cause battery performance sharply to decline, material storage and industrialization in terms of cause difficulty, using silicon
Alkane coupling agent kh560 cladding can effectively reduce moisture absorption phenomenon, improve the water resistance of material, and can improve material thermal stability and
Mechanical stability.
Tertiary cathode material silane coupling agent in the preferred embodiment of the present invention, after proton acid phosphoric acid is washed
Kh560 cladding, tertiary cathode material surface are formed two layers of clad, and one layer is Li3PO4Clad, one layer is kh560 packet
Coating, the clad for being formed by even compact not only effectively block the hair of electrolyte and original material surface mass side reaction
It is raw, while the percent of pass of lithium ion deintercalation is improved, greatly promote the cycle performance of material.
In one preferred embodiment, the dosage of silane coupling agent is silane coupling agent and the matter for washing rear positive electrode
Amount is than being 1:99.The fabulous cycle performance of the materials serve of this covering amount, not only recycles under high capacity, but also coulombic efficiency
It also improves.
The inventors discovered that lower covering amount does not form fine and close clad when the dosage of silane coupling agent is lower,
Hydrophobic ability decline, it is poor to HF resilience in electrolysis.When the amount of silane coupling agent is excessive, thicker clad follows material
The improving effect of ring performance is simultaneously little, illustrates blocked up clad, not only hinders the deintercalation of internal lithium ion, also makes battery table
Face activity reduce, cause material the later period structural instability of circulation be capacity attenuation quickly.
In the present invention, the post-processing includes first dispersing covering dispersing agent II, then wash rear anode for what is weighed up
Material is added in scattered covering, removes dispersing agent II, is dried in vacuo, and heat treatment obtains final products.
The dispersing agent II is alcohols, and preferably methanol, ethyl alcohol, isopropanol are more selected as ethyl alcohol, further preferably without
Water-ethanol；
In one preferred embodiment, disperse silane coupling agent kh560 with dehydrated alcohol, it is super with Ultrasound Instrument when dispersion
Sound dispersion, preferably ultrasonic disperse 2h, so that silane coupling agent is uniformly distributed, to reach equal in ternary material after cladding is washed
Even and fine and close cladding.
The inventors discovered that the mode for removing dehydrated alcohol is not particularly limited, oil bath heating is used in the present invention, normal pressure steams
Hair falls dehydrated alcohol, and evaporating temperature is 60~80 DEG C.
In one preferred embodiment, the evaporating temperature for removing dehydrated alcohol is 70 DEG C.
In the present invention, the vacuum drying is 65~85 DEG C, and preferably 80 DEG C, the vacuum drying time is 3~8h,
Preferably 4~6h；
The inventors discovered that the ternary material after pickling is after silane coupling agent cladding, Yao Jinhang low-temperature vacuum drying is done
Dry temperature is 65~85 DEG C, and drying time is preferably 4~6h, effectively removes remaining dispersing agent ethyl alcohol.
In the present invention, it is described heat treatment for vacuum drying, vacuum drying temperature be 100~200 DEG C, the time be 2~
7h, preferably 3~5h.
The inventors discovered that the ternary material after cladding after low temperature drying, will be also further heat-treated, compared with
Allow silane coupling agent is strong to be adhered on positive electrode under high-temperature.
It is provided by the invention that there is the nickelic tertiary cathode material for improving electrical property, it is made according to above-mentioned method, institute
The battery of positive electrode preparation is stated within the scope of 3.0V~4.3V with 1C rate charge-discharge, initial discharge specific capacity reaches 177mAh/
G or more；And/or
The battery of positive electrode preparation within the scope of 3.0V~4.3V with after 1C circulation 200 times, coulombic efficiency
It is 85% or more.
In the preferred embodiment of the present invention, what is be prepared has the nickelic tertiary cathode material surface for improving electrical property
Two layers of clad is formd, one layer is Li3PO4Clad, one layer is kh560 clad, is formed by the clad of even compact
The generation of electrolyte and original material surface mass side reaction is not only effectively blocked, while improving passing through for lithium ion deintercalation
Rate greatly promotes the cycle performance of material, effectively increases electrical property.
Embodiment
The present invention is further described below by way of specific example.But these examples are only exemplary, not to this
The protection scope of invention constitutes any restrictions.
Embodiment 1
Phosphoric acid 0.05g is dispersed in dehydrated alcohol 10mL at room temperature first, stirs 0.5h.Again by Li
(Ni0.8Co0.1Mn0.1)O2Powder 5g (mass ratio of positive electrode matrix and phosphoric acid is 99:1) is slowly poured into scattered molten
In liquid, in oil bath with the stirring evaporation of 80 DEG C of constant temperature, after ethyl alcohol all evaporation, by the powder after proton pickling in air with
500 DEG C of calcining at constant temperature 5h, cooling, obtained system is 5.02g or so, number NCM-a1；
By the kh560 (according to the mass ratio 99.5:0.5 of tertiary cathode material and kh560 after pickling) of 0.025g shifting
Liquid rifle pipettes kh560, is added in the dehydrated alcohol of 15ml and uses ultrasonic disperse 2h, is transferred in capacity, then the step 1 that will be weighed up
Obtained system 5.02g is poured into volumetric flask, is stirred and is evaporated in 60-80 DEG C of oil bath, then by the material after cladding in vacuum
Drying box is in 80 DEG C of 5 hours of baking；
By obtained mixture 100-200 DEG C of heat treatment 4h in a vacuum drying oven, it is silane coupled for obtaining final product
Li (the Ni of agent kh560 cladding0.8Co0.1Mn0.1)O2Tertiary cathode material, number NCM-a1-k0.5.
Embodiment 2
Experimental procedure is same as Example 1, and difference is that the dosage of kh560 used is 0.0507g (with ternary after pickling
The mass ratio of positive electrode is 1:99), number NCM-a1-k1.
Embodiment 3
Experimental procedure is same as Example 1, and difference is that the dosage of kh560 used is 0.1024g (with ternary after pickling
The mass ratio of positive electrode is 2:98), number NCM-a1-k2.
Embodiment 4
Experimental procedure is same as Example 1, and difference is that the dosage of phosphoric acid used is 0.07614g (with tertiary cathode material
The mass ratio for expecting matrix is 1.5:98.5), silane coupling agent Kh560 is the 0.055g (quality with tertiary cathode material after pickling
Than for 1:99), number NCM-a1.5-k1.
Embodiment 5
Experimental procedure is same as Example 1, and difference is that the dosage of phosphoric acid used is 0.0251g (with tertiary cathode material
The mass ratio of matrix is 0.5:99.5), silane coupling agent Kh560 is the 0.0507g (quality with tertiary cathode material after pickling
Than for 1:99), number NCM-a0.5-k1.
Comparative example
Comparative example 1
Oxalic acid 0.05g is dispersed in dehydrated alcohol 10mL at room temperature first, stirs 0.5h.Again by Li
(Ni0.8Co0.1Mn0.1)O2Powder 5g (mass ratio of positive electrode matrix and oxalic acid is 99:1) is slowly poured into scattered molten
In liquid, in oil bath with the stirring evaporation of 80 DEG C of constant temperature, after ethyl alcohol all evaporation, by the powder after proton pickling in air with
500 DEG C of calcining at constant temperature 5h, it is cooling, ternary material after pickling is obtained, number is NCM (oxalic acid)；
It is that 0.0507g (mass ratio according to NCM (oxalic acid) and kh560 is 99:1) is pipetted with liquid-transfering gun by kh560
Kh560 is added in the dehydrated alcohol of 5ml with ultrasonic disperse 2h, is transferred in capacity, then by the NCM weighed up (oxalic acid) 5.02g
It pours into volumetric flask, stirs and be evaporated in 60-80 DEG C of oil bath, then the material after cladding is dried 5 at 80 DEG C in vacuum oven
A hour；
By obtained mixture 100-200 DEG C of heat treatment 4h in a vacuum drying oven, it is silane coupled for obtaining final product
Li (the Ni of agent kh560 cladding0.8Co0.1Mn0.1)O2Tertiary cathode material, number are NCM- oxalic acid-k1.
Comparative example 2
Acetic acid 0.05g is dispersed in dehydrated alcohol 10mL at room temperature first, stirs 0.5h.Again by Li
(Ni0.8Co0.1Mn0.1)O2Powder 5g (mass ratio of positive electrode matrix and acetic acid is 99:1) is slowly poured into scattered molten
In liquid, in oil bath with the stirring evaporation of 80 DEG C of constant temperature, after ethyl alcohol all evaporation, by the powder after proton pickling in air with
500 DEG C of calcining at constant temperature 5h, cooling, the ternary material after obtaining pickling, number is NCM (acetic acid)；
It is that 0.0507g (mass ratio according to NCM (acetic acid) and kh560 is 99:1) is pipetted with liquid-transfering gun by kh560
Kh560 is added in the dehydrated alcohol of 5ml with ultrasonic disperse 2h, is transferred in capacity, then by the NCM weighed up (acetic acid) 5.02g
It pours into volumetric flask, stirs and be evaporated in 60-80 DEG C of oil bath, then the material after cladding is dried 5 at 80 DEG C in vacuum oven
A hour；
By obtained mixture 100-200 DEG C of heat treatment 4h in a vacuum drying oven, final product silane coupling agent is obtained
Li (the Ni of kh560 cladding0.8Co0.1Mn0.1)O2Tertiary cathode material, number are NCM- acetic acid-k1.
Comparative example 3
Lithium dihydrogen phosphate 0.05g is dispersed in dehydrated alcohol 10mL at room temperature first, stirs 0.5h.Again by Li
(Ni0.8Co0.1Mn0.1)O2Powder 5g (mass ratio of positive electrode matrix and lithium dihydrogen phosphate is 99:1) is slowly poured into dispersion
In good solution, in oil bath with 80 DEG C of constant temperature stirring evaporations, after ethyl alcohol all evaporation, by the powder after proton pickling in sky
With 500 DEG C of calcining at constant temperature 5h in gas, cooling, the ternary material after being washed, number is NCM (lithium dihydrogen phosphate)；
It is that 0.0507g (mass ratio according to NCM (lithium dihydrogen phosphate) and kh560 is 99:1) is moved with liquid-transfering gun by kh560
Kh560 is taken, is added in the dehydrated alcohol of 5ml and uses ultrasonic disperse 2h, be transferred in capacity, then the NCM (biphosphate that will be weighed up
Lithium) 5.02g is poured into volumetric flask, is stirred and be evaporated in 60-80 DEG C of oil bath, then the material after cladding is existed in vacuum oven
80 DEG C of 5 hours of baking；
By obtained mixture 100-200 DEG C of heat treatment 4h in a vacuum drying oven, final product silane coupling agent is obtained
Li (the Ni of kh560 cladding0.8Co0.1Mn0.1)O2Tertiary cathode material, number are NCM- lithium dihydrogen phosphate-k1.
Comparative example 4
Experimental procedure is same as Example 2, and difference is that covering used is kh550, and dosage is 0.0507g (with three
The mass ratio of first positive electrode matrix is 1:99), number NCM-a1-k550.
Comparative example 5
Experimental procedure is same as Example 2, and difference is that covering used is kh570, and dosage is 0.0507g (with three
The mass ratio of first positive electrode matrix is 1:99), number NCM-a1-k570.
Comparative example 6
It is that 0.0251g (mass ratio according to original material NCM811 and kh560 is 99.5:0.5) uses liquid-transfering gun by kh560
Kh560 is pipetted, is added in the dehydrated alcohol of 5ml and uses ultrasonic disperse 2h, be transferred in capacity, then untreated by what is weighed up
NCM811 is that 5g is poured into volumetric flask, stirs and is evaporated in 60-80 DEG C of oil bath, then by the material after cladding in vacuum oven
In 80 DEG C of 5 hours of baking；
By obtained mixture 100-200 DEG C of heat treatment 4h in a vacuum drying oven, final product silane coupling agent is obtained
Li (the Ni of kh560 cladding0.8Co0.1Mn0.1)O2Tertiary cathode material, number NCM-k0.5.
Comparative example 7
For step with comparative example 6, difference is that kh560 used is 0.0505g (according to mass ratio 99:1), number NCM-
k1。
Comparative example 8
For step with comparative example 6, difference is that kh560 used is 0.101g (according to mass ratio 99:2), number NCM-
k2。
Comparative example 9
It is that 0.0505g (mass ratio according to original material NCM811 and kh550 is 99:1) is moved with liquid-transfering gun by kh550
Kh550 is taken, is added in the dehydrated alcohol of 5ml and uses ultrasonic disperse 2h, be transferred in capacity, then untreated by what is weighed up
NCM811 is that 5g is poured into volumetric flask, stirs and is evaporated in 60-80 DEG C of oil bath, then by the material after cladding in vacuum oven
In 80 DEG C of 5 hours of baking；
By obtained mixture 100-200 DEG C of heat treatment 4h in a vacuum drying oven, final product silane coupling agent is obtained
Li (the Ni of kh550 cladding0.8Co0.1Mn0.1)O2Tertiary cathode material, number NCM-k550.
Comparative example 10
For step with comparative example 9, difference is that kh570 used is 0.0505g (according to original material NCM811 and kh570
Mass ratio 99:1), number NCM-k570.
" (ternary) positive electrode matrix " described herein is equivalent in meaning with " original material ".
Experimental example
The SEM of 1 different materials of experimental example schemes
Fig. 1 is the SEM figure that original material NCM811 and original material NCM811 coats different amounts of kh560；The latter comes from
In the product of 6~comparative example of comparative example 8.
Fig. 2 is the SEM figure that different amounts of kh560 is coated by the NCM811 that 1% phosphoric acid is handled.Fig. 2 material therefor comes from
In the product of 1~embodiment of embodiment 3.
In Fig. 1,
811 show the SEM figure of original material NCM811；
0.5% shows the SEM figure of NCM-k0.5 made from comparative example 6；
1% shows the SEM figure of NCM-k1 made from comparative example 7；
2% shows the SEM figure of NCM-k2 made from comparative example 8；
In Fig. 2,
K-0.5% shows the SEM figure of NCM-a1-k0.5 made from embodiment 1；
K-1% shows the SEM figure of NCM-a1-k1 made from embodiment 2；
K-2% shows the SEM figure of NCM-a1-k2 made from embodiment 3.
From figure 1 it appears that the primary particle of untreated original material NCM811 material is slab-like, in covering amount
When being 0.5%, it can be observed that surface platelets object becomes more tiny from Fig. 1, when amplifying 5k times, a other particle is wrapped
It covers, and other granule-morphologies do not change, when illustrating that covering amount is 0.5%, only a other particle has clad.When
When covering amount is increased to 1%, this it appears that primary particle surface becomes dense uniform from Fig. 1, as one layer of mucilage binding substance
It is covered on surface, enlargement ratio finds that most spheric granules surface is capped one layer of fine and close clad after turning down.When
When covering amount is 2%, observe in Fig. 1, primary particle sheet degree is smaller, but many particle pictures can be found by one layer of jelly
Reunite together, but the particle sphericity under all different covering amounts is intact, illustrates that cladding only changes particle surface
Pattern does not impact structure.
As can be seen from Figure 2 when the NCM811 material by the processing of 1% phosphoric acid coats silane coupling agent kh560 again, material
Material still keeps good sphericity, and partial size is about 12 μm, and particle is uniformly dispersed and surface becomes smooth densification, not extra
Impurity generates, and gelatinous clad is presented in surface.
The XRD diagram of 2 different materials of experimental example
Fig. 3 shows original material NCM811 and original material NCM811 coats the XRD diagram of different amounts of kh560 material.
The NCM811 that Fig. 4 shows after original material NCM811 and pickling coats the XRD diagram of different amounts of kh560 material.
In Fig. 3,
A shows the XRD curve of NCM-k0.5 made from comparative example 6；
B shows the XRD curve of NCM-k1 made from comparative example 7；
C shows the XRD curve of NCM-k2 made from comparative example 8；
D shows the XRD curve of original material NCM811.
In Fig. 4,
A shows the XRD curve of NCM-a1-k0.5 made from embodiment 1；
B shows the XRD curve of NCM-a1-k1 made from embodiment 2；
C shows the XRD curve of NCM-a1-k2 made from embodiment 3；
D shows the XRD curve of original material NCM811.
From figure 3, it can be seen that the position at each peak illustrates that the material of cladding does not change there is no variation before and after cladding
Become the structure of raw material, and each has good α-NaFeO2Layer structure belongs to R-3m space group.Layer structure ratio
Significantly (018/110), the division of (006/102) these two pair peak is still it is obvious that illustrate the material crystalline degree of cladding front and back very
It is good, it is shown in Table 1 (the wherein cell parameter that a, c represent material).
The lattice parameter of table 1 NCM811 and the material of different covering amounts
| Material | a | c | c/a | I003/I104 |
| NCM811 | 2.8775 | 14.2434 | 4.949 | 1.36 |
| NCM-k0.5 | 2.8776 | 14.2532 | 4.9531 | 1.34 |
| NCM-k1 | 2.8773 | 14.2547 | 4.9541 | 1.35 |
| NCM-k2 | 2.878 | 14.2573 | 7.9538 | 1.33 |
As can be seen from Figure 4 four kinds of materials still fall within six side's layer structures, R-3m space group, and 006/102 and 018/
110 bimodal splitting degrees are good, and the material after illustrating cladding still keeps good layer structure.It is not observed silane coupled
The diffraction maximum of agent, first is that probably due to kh560 is non-crystal structure, second is that not reaching minimum because the amount of cladding is too small
Detection line.To with after the software refine of XRD data measured, available a, c value, while can also be calculated by software
The value of I003/I104, to judge cationic mixing degree.Obtained data are converged and table 2.As can be seen from the table, after cladding
A, c value of material are above original material.
The lattice parameter of 2 NCM811 of table and the material of covering amounts different after pickling
| Material | a | c | c/a | I003/I104 |
| NCM811 | 2.8763 | 14.2436 | 4.9521 | 1.38 |
| NCM-a1-k0.5 | 2.8775 | 14.2534 | 4.9534 | 1.36 |
| NCM-a1-k1 | 2.8771 | 14.2537 | 4.9542 | 1.33 |
| NCM-a1-k2 | 2.8777 | 14.2572 | 4.9544 | 1.34 |
By calculating, the c/a value of four kinds of materials is respectively 4.9521,4.9534,4.9542,4.9544, it can be seen that with
The increase of covering amount, the unit cell volume of material is also with increase.In addition, I003/I104 is all larger than 1.2 before and after cladding, say
Li in bright structure+With Ni2+It is all smaller in interlayer extent of migration, but I003/I104 is more cationic than original material after cladding
Mixing degree is larger.
The high rate performance curve of 3 different materials of experimental example
Fig. 5 shows untreated original material NCM811 and original material NCM811 coats the multiplying power of different amounts of kh560
Performance curve.By resulting covering material and original material packed battery, and electro-chemical test is carried out at normal temperature, in 3.0-
In 4.3V voltage range, 0.1C, 0.5C, 1C are tested respectively, 2C, 3C, the high rate performance under 5C.
In Fig. 5,
A shows the high rate performance curve of NCM-k0.5 made from comparative example 6；
B shows the high rate performance curve of NCM-k1 made from comparative example 7；
C shows the high rate performance curve of NCM-k2 made from comparative example 8；
D shows the high rate performance curve of original material NCM811.
Fig. 6 shows the NCM811 after untreated original material NCM811 and pickling and coats times of different amounts of kh560
Rate performance curve.When carrying out high rate performance test, four kinds of materials first activated at 0.1C three times, respectively 0.5C,
Constant-current discharge under the conditions of 1C, 2C, 3C, 5C recycles 5 times under every kind of multiplying power.
In Fig. 6,
A shows the high rate performance curve of NCM-a1-k0.5 made from embodiment 1；
B shows the high rate performance curve of NCM-a1-k1 made from embodiment 2；
C shows the high rate performance curve of NCM-a1-k2 made from embodiment 3；
D shows the high rate performance curve of original material NCM811.
From figure 5 it can be seen that the specific capacity and original material when covering amount is 0.5% under difference discharge-rate are discharged
Specific capacity is close, is not improved, and analysis is that the amount of cladding causes the uneven of cladding not play the role of clad very little,
In 5C electric discharge, specific capacity is lower than original material instead, may be that non-uniform clad hinders height in conjunction with SEM map analysis
The deintercalation of lithium ion, declines chemical property under multiplying power.
When covering amount is 1%, high rate performance highest, 0.1C, O.5C, 1C, 2C, multiplying power is respectively reached under 3C, 5C
198.11mAh/g, 183.53mAh/g, 175.64mAh/g, 165.02mAh/g, 155.65mAh/ g, 137.33mAh/g compare
Original material capacity is high, this is that silane coupling agent macromolecular chain is mutually bonded the three-dimensional net structure being cross-linked into, and makes the resistance to of material
Aqueous, thermal stability and mechanical property are promoted, and inert clad has certain inhibiting effect to the HF acid in electrolyte,
Improve the high rate performance of material.
In Fig. 6, four kinds of materials first activate three times at 0.1C, and constant current is put under the conditions of respectively in 0.5C, 1C, 2C, 3C, 5C
Electricity recycles 5 times under every kind of multiplying power, and specific discharge capacity is respectively under original material 0.1C, 0.5C, 1C, 2C, 3C, 5C current density
185mAh/g, 175mAh/g, 167mAh/g, 156mAh/g, 146mAh/g, 130mAh/g.And the material when covering amount is 1%
Material shows best high rate performance, and specific discharge capacity is respectively 208mAh/g at 0.1C, 0.5C, 1C, 2C, 3C, 5C,
193mAh/g, 185mAh/g, 174mAh/g, 165mAh/g, 146mAh/g illustrate that 1% covering amount can make silane coupling agent
- Si-O-C- key ,-C-O-C- key and epoxy bond in kh560 are capable of forming one layer of netted clad structure, make the biography of lithium ion
Conductance improves, and in addition the hydrophobicity of silane coupling agent can reduce material water sucting degree in homogenization process, and material is enable to exist
Higher specific discharge capacity can also be discharged under high current density.It is the electrochemistry of 0.5% and 2% material by test covering amount
Can, although the performance compared with original material increases, with the increase of current density, the material property of 2% covering amount declines
Quickly, illustrate that cladding is too thick, the deintercalation of lithium ion can be hindered.The material of 0.5% covering amount is simultaneously compared with the specific discharge capacity after pickling
It does not improve too much, illustrates that clad is too thin, material cannot be made to form the clad of uniform compact, do not play silane coupling agent
Advantage.
The cycle performance curve of 4 different materials of experimental example
Fig. 7 shows the cycle performance song that original material NCM811 and original material NCM811 coats different amounts of kh560
Line；
The NCM811 that Fig. 8 shows original material NCM811 and pickling coats the cycle performance curve of different amounts of kh560.
In Fig. 7,
A shows the cycle performance curve of NCM-k0.5 made from comparative example 6；
B shows the cycle performance curve of NCM-k1 made from comparative example 7；
C shows the cycle performance curve of NCM-k2 made from comparative example 8；
D shows the cycle performance curve of original material NCM811.
In Fig. 7, a, d curve is essentially coincided, and is located at below b curve.
In Fig. 8,
A shows the cycle performance curve of NCM-a1-k0.5 made from embodiment 1；
B shows the cycle performance curve of NCM-a1-k1 made from embodiment 2；
C shows the cycle performance curve of NCM-a1-k2 made from embodiment 3；
D shows the cycle performance curve of original material NCM811.
In Fig. 7, under 1C cycling condition, original material and covering amount are that 0.5%, 1%, 2% first discharge specific capacity is
168.61mAh/g, 167.2mAh/g, 174.67mAh/g, 166.61mAh/g, capacity is respectively after recycling 200 times
142.7656mAh/g, 141.2253 mAh/g, 146.3617mAh/g, 140.7656mAh/g, cycle efficieny 84.67%,
84.46%, 83.79%, 84.49%.From data it can be seen that when only covering amount is 1%, the specific capacity of 1C circulation is
It is promoted, but in terms of cycle efficieny, the slope of the capacity attenuation of the material after cladding is close with original material, in the circulating cycle, just opens
Kh560 is reacted with water remaining in electrolyte when beginning, intermolecular dehydration occurs, reaction equation:
But with the progress of reaction, especially under high current, battery temperature is increased, and kh560 itself can be made also to occur de-
Water condensation reaction, i.e. kh560 self-crosslinking reaction, self-crosslinking reaction can reduce kh560 to the resilience of the HF of electrolyte, cause
The remaining LiOH and LiCO3 on high-nickel material surface are reacted with electrolyte HF acid makes battery heating rate faster, kh560 self-crosslinking
Rate it is directly proportional to the temperature of reaction, form vicious circle, therefore to reduce the speed of silane coupling agent self-crosslinking reaction, can
To lower the temperature of battery, to inhibit the progress of cross-linking reaction by the compound for the remaining lithium for reducing high-nickel material surface.
In Fig. 8, when carrying out four kinds of material circulation performance tests, for voltage range in 3.0-4.3V, present 0.1C electric current is close
Lower 3 circle of activation of degree, recycles 200 times at 1C, and original material first discharge specific capacity at 1C is 169mAh/g, is recycled 200 times
Specific discharge capacity is 143 mAh/g afterwards, and coulombic efficiency 84.54%, the material of covering amount 0.5%, 1%, 2% is in 1C head
Secondary specific discharge capacity is respectively 179mAh/g, 186mAh/g, and 177mAh/g, after circulation 200 times, specific discharge capacity is respectively
163mAh/g, 174mAh/g, 151mAh/g, coulombic efficiency are respectively 91.28%, 93.42%, 85.32%.Material after pickling
After material cladding silane coupling agent, the cycle performance of material all promoted, and the materials serve that wherein covering amount is 1% is fabulous
Cycle performance not only recycles under high capacity, but also coulombic efficiency also improves, when covering amount is 0.5%.Stable circulation performance
Enhancing, but that specific capacity does not have covering amount is high when being 1%, illustrates that lower covering amount does not form fine and close clad, hydrophobic energy
After power declines, poor to HF resilience in electrolysis, but phosphoric acid is washed, the Li of surface formation3PO4Clad reduces in electrolysis HF pairs
The solubility of material, circulation makes battery maintain preferable stability under high magnification.When covering amount is 2%, clad pair
The improving effect of material circulation performance is simultaneously little, illustrates blocked up clad, not only hinders the deintercalation of internal lithium ion, also makes
Battery surface activity reduce, cause material the later period structural instability of circulation be capacity attenuation quickly.
It is as follows that table 3 is made by the data that Fig. 7 and Fig. 8 are obtained:
The specific discharge capacity and cycle efficieny data comparison table of 3 different materials of table
By 1% phosphoric acid it can be seen from Fig. 7, Fig. 8 and table 3 wash original material NCM811 after coat silane coupling agent kh560
Afterwards, so that the cycle performance of battery greatly improves, especially NCM-a1-k1 made from embodiment 2, cycle efficieny are improved about
10%.
The TEM of 5 ternary material NCM-a1-k1 of experimental example schemes
Fig. 9 shows 1% phosphoric acid and washes after NCM811 acquired NCM-a1-k1 after the silane coupling agent kh560 of cladding 1%
TEM figure.Wherein,
Fig. 9 (a) shows the TEM figure of original material NCM811；
Fig. 9 (b) shows the TEM figure of NCM-a1-k1 made from embodiment 2.
Find out from Fig. 9 (b), one layer of about Li of 5nm3PO4Clad and one layer of kh560 clad for 5nm.Uniformly
Fine and close clad effectively stops the generation of electrolyte and original material surface mass side reaction, while improving lithium ion deintercalation
Percent of pass, promote the cycle performance of material.
The cycle performance curve of kh560 is coated after the different proton pickling NCM811 material of experimental example 6 and pickling
Figure 10 shows the cycle performance curve graph of the NCM811 material of same amount of different Bronsted acid pickling.Wherein,
A shows the cycle performance curve of NCM-a1 made from step 1 in embodiment 1 (embodiment 2)；
B shows the cycle performance curve of NCM- oxalic acid made from step 1 in comparative example 1；
C shows the cycle performance curve of NCM- acetic acid made from step 1 in comparative example 2.
Figure 11 shows the cycle performance curve of cladding Kh560 after different proton pickling NCM811
Wherein,
A shows the cycle performance curve of NCM-a1-k1 made from embodiment 2；
B shows the cycle performance curve of NCM- oxalic acid-k1 made from comparative example 1；
C shows the cycle performance curve of NCM- acetic acid-k1 made from comparative example 2.
It is best from Figure 10 high temperature 50 weeks loop-around datas of circulation and Figure 11 it is found that the cycle performance of oxalic acid pickling is worst
Be phosphoric acid pickling；The material circulation performance of 1% phosphoric acid pickling NCM811 material cladding kh560 is best, followed by acetic acid,
This is because one side oxalic acid acidity is excessive, it is stronger to material surface corrosivity；Another aspect phosphoric acid and LiOH and Li2CO3Reaction
When can disposably consume 3 Li+Form Li3PO4, it is a kind of good ion conductor (6*10-8S/cm), this is effectively protected
Body material is not by the corrosion of HF in electrolyte.And phosphoric acid is washed afterwards and the product of cladding kh560 can be in NCM811 material surface
Form two layers of clad, one layer of about Li of 5nm3PO4Clad and one layer of kh560 clad for 5nm.The packet of even compact
Coating effectively stops the generation of electrolyte and original material surface mass side reaction, while improving passing through for lithium ion deintercalation
Rate promotes the cycle performance of material.
The cycle performance of the different silane coupling agent cladding original material NCM811 of experimental example 7 and the NCM811 of pickling are bent
Line
Figure 12 shows the cycle performance curve of different silane coupling agent cladding NCM811；
Wherein,
A shows the cycle performance curve of NCM-k1 made from comparative example 7；
B shows the cycle performance curve of NCM-k550 made from comparative example 9；
C shows the cycle performance curve of NCM-k570 made from comparative example 10.
Figure 13 shows the cycle performance curve of the NCM811 after different silane coupling agent cladding pickling.Wherein,
A shows the cycle performance curve of NCM-a1-k1 made from embodiment 2；
B shows the cycle performance curve of NCM-a1-k550 made from comparative example 4；
C shows the cycle performance curve of NCM-a1-k570 made from comparative example 5.
After it can be seen that whether cladding original material NCM811 in Figure 12 and Figure 13 or coat pickling
The cycle performance of the material of NCM811, silane coupling agent kh560 cladding is best, and followed by kh550 illustrates that kh560 is played very
Good physical barrier effect, increases cladding intensity, the high-temperature stability of reinforcing material.
8 phosphoric acid pickling of experimental example and lithium dihydrogen phosphate wash the cycle performance curve of cladding kh560 after NCM811
In Figure 14,
A shows the cycle performance curve of NCM-a1-k1 made from embodiment 2；
B shows the cycle performance curve of NCM- lithium dihydrogen phosphate-k1 made from comparative example 3.
As can be seen from Figure 14 with the cycle performance of material after phosphoric acid pickling obviously than good, the capacity with lithium dihydrogen phosphate
Also relatively higher.On the one hand illustrating phosphoric acid after pickling reduces the residual alkali of material surface, on the other hand can be with the trip of material surface
Li is generated from lithium3PO4, effective protection ontology NCM811 material.
The different amounts of phosphoric acid of experimental example 9 washes the cycle performance curve of cladding kh560 after NCM811
Figure 15 shows the cycle performance curve that different amounts of phosphoric acid washes NCM811 cladding kh560, wherein
A shows the cycle performance curve of NCM-a1-k1 made from embodiment 2；
B shows the cycle performance curve of NCM-a0.5-k1 made from embodiment 5；
C shows the cycle performance curve of NCM-a1.5-k1 made from embodiment 4.
As can be seen from Figure 15, it is best to wash the material circulation performance that cladding kh560 is obtained after NCM811 for 1% phosphoric acid,
0.5% phosphoric acid takes second place.When this illustrates that phosphoric acid dosage is excessively high, positive electrode surface can be caused to corrode, serious destruction material
Pattern, to cause the missing of lithium ion inside positive electrode, crystal structure is destroyed, and influences positive electrode electrical property, not only not
The electrical property of ternary material can be improved, will be greatly reduced the electrical property of ternary material instead.When phosphoric acid dosage is too small, and cannot
Remaining LiOH and Li is effectively reduced2CO3Amount, thus the electrical property of ternary material cannot be improved.
Thus illustrate, through this method be prepared with improve electrical property nickelic tertiary cathode material have compared to
The original better electrical property of nickelic positive electrode；Meanwhile after covering is handled, the hydrophobicity of nickelic positive electrode is obtained more
Good promotion.It is preferred that when being washed with phosphoric acid and coating kh560, the Li of the even compact of formation3PO4It is effective with kh560 double-coating layer
The generation of electrolyte and original material surface mass side reaction is blocked, while improving the percent of pass of lithium ion deintercalation, makes material
The cycle performance of material is promoted, and effectively increases the electrical property of nickelic positive electrode.
It is described the invention in detail above in conjunction with detailed description and exemplary example, but these explanations are simultaneously
It is not considered as limiting the invention.It will be appreciated by those skilled in the art that without departing from the spirit and scope of the invention,
Can be with various equivalent substitutions, modifications or improvements are made to the technical scheme of the invention and its embodiments, these each fall within the present invention
In the range of.Scope of protection of the present invention is subject to the appended claims.
Claims (10)
1. a kind of with the nickelic tertiary cathode material for improving electrical property, which is characterized in that the positive electrode is by positive electrode
Matrix is obtained through overpickling and cladding.
2. nickelic tertiary cathode material according to claim 1, which is characterized in that the positive electrode matrix is by formula Li
(Ni1-x-yCoxMny)O2It indicates, wherein 0,0.4 > y > 0 of 1-x-y >=0.5,0.4 > x >, it is preferable that positive electrode matrix is
Li(Ni0.8Co0.1Mn0.1)O2。
3. the preparation method with the nickelic tertiary cathode material for improving electrical property, which comprises the following steps:
Step 1, positive electrode matrix is added in Bronsted acid dispersion liquid, is stirred, remove dispersing agent；
Step 2, the system that step 1 obtains is calcined, obtains washing rear positive electrode；
Step 3, rear positive electrode will be washed to mix with covering, and will post-process, obtains final products.
4. according to the method described in claim 3, it is characterized in that, the positive electrode matrix is by Li (Ni in step 11-x- yCoxMny)O2It indicates, wherein 0,0.4 > y > 0 of 1-x-y >=0.5,0.4 > x >, the positive electrode matrix is preferably Li
(Ni0.8Co0.1Mn0.1)O2。
5. according to the method described in claim 3, it is characterized in that, in step 1, the Bronsted acid is acetic acid, oxalic acid or phosphoric acid,
Preferably phosphoric acid；
The mass ratio of the Bronsted acid and positive electrode matrix is (0.001~1): 100, preferably (0.005~0.05): 100,
Further preferably 0.5:99.5,1:99,1.5:98.5 or 2:98 are still more preferably 1:99.
6. according to the method described in claim 3, it is characterized in that, the Bronsted acid dispersion liquid is used for Bronsted acid to be divided in step 1
Powder disperses to obtain, and the dispersing agent is alcohols, preferably methanol, ethyl alcohol or isopropanol, more preferably ethyl alcohol, further preferably
For dehydrated alcohol；
The temperature for removing dispersing agent is 70~90 DEG C.
7. according to the method described in claim 3, it is characterized in that, the calcination temperature is 450-550 DEG C, preferably in step 2
It is 500 DEG C,
The calcination time is 4-6h, preferably 5h.
8. according to the method described in claim 3, it is characterized in that, the covering is silane coupling agent, preferably in step 3
For kh550, kh560 or kh570, further preferably kh560,
The dosage of the silane coupling agent is silane coupling agent and washes the mass ratio of rear positive electrode as (0.001~1): 100, it is excellent
Be selected as (0.005~0.05): 100, further preferably 0.5:99.5,1:99 or 2:98 are still more preferably 1:99.
9. according to the method described in claim 3, it is characterized in that, the post-processing includes first using covering to divide in step 3
Powder II dispersion, then the rear positive electrode of washing weighed up is added in scattered covering, it is uniformly mixed, removes dispersing agent
II is dried in vacuo, and heat treatment obtains final products.
10. according to the method described in claim 9, it is characterized in that, the dispersing agent II be alcohols, preferably methanol, ethyl alcohol,
Isopropanol, more preferably ethyl alcohol, further preferably dehydrated alcohol；
The vacuum drying is 65~85 DEG C, and preferably 80 DEG C, the vacuum drying time is 3~8h, preferably 4~6h；
The heat treatment is vacuum drying, and vacuum drying temperature is 100~200 DEG C, and the time is 2~7h, preferably 3~5h.
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