CN108011100A - A kind of tertiary cathode material of surface reaction cladding and preparation method thereof - Google Patents
A kind of tertiary cathode material of surface reaction cladding and preparation method thereof Download PDFInfo
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- CN108011100A CN108011100A CN201711353382.6A CN201711353382A CN108011100A CN 108011100 A CN108011100 A CN 108011100A CN 201711353382 A CN201711353382 A CN 201711353382A CN 108011100 A CN108011100 A CN 108011100A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
Tertiary cathode material the invention discloses a kind of surface reaction cladding and preparation method thereof, is related to field of lithium ion battery.The preparation method of positive electrode provided by the invention comprises the following steps：Under normal temperature condition, surface reaction covering is placed in milling apparatus with tertiary cathode material powder, grinding makes it obtain mixture after mixing；The mixture is placed in tube-type atmosphere furnace, heats up and heat preservation sintering obtains primary product；After the primary product is ground, 400 mesh sieves are crossed, obtain final product.The preparation method of positive electrode provided by the invention can form clad on its surface and effectively reduce the alkalinity in positive electrode, and the gas of pollution environment will not be produced in preparation process, and the rotproofness requirement for equipment is relatively low；The positive electrode provided by the invention prepared by this method has higher specific capacity and capacity retention ratio.
Description
Technical field
The present invention relates to field of lithium ion battery, more particularly to a kind of tertiary cathode material of surface reaction cladding
And preparation method thereof.
Background technology
As the green high-capacity battery of a new generation, lithium ion battery have weight is small, energy density is high, have extended cycle life,
The advantages such as operating voltage height, memory-less effect, non-environmental-pollution, are widely used to mobile phone, laptop, video camera etc. just
Take in formula electronic equipment, and following electric automobile and the preferable electrical source of power of mixed type electric automobile, there is wide answer
Use prospect.
Commercial Li-ion battery generally use has layer structure LiCoO2Make positive electrode, but since it overcharges meeting
Layer structure is caused to collapse, so its actual reversible capacity only has the 56% of theoretical capacity.The resource of cobalt is limited, expensive,
Therefore, exploitation is necessary with height ratio capacity, the positive electrode of low price.Nickelic based material is due to specific discharge capacity
The advantages that high, cheap, which is expected to become, substitutes LiCoO2Positive electrode, LiNi0.8C0.15Al0.05O2Pass through cobalt and aluminium ion
Co-doped after drastically increase its stratiform stability, show more excellent electrochemistry and thermodynamic stability, put
Electric specific capacity is up to 200mAh/g, is one of material of greatest concern in current nickelic cathode.
At present, tertiary cathode material still has some problems in use, since its nickel content is higher, is filled in height
Cyclical stability under piezoelectric voltage condition and hot conditions is bad.In anode sizing agent preparation process, due to nickelic positive electrode surface
The relatively low nickel positive electrode higher of remaining alkali content, in atmosphere exposure a period of time will the moisture absorption so as to causing adhesive failure
As g., jelly-like, the painting process of such slurry will be unable to carry out, and raw material can only be scrapped, and greatly cause manpower and materials
Waste.In addition, surface residual alkaline impurities easily and air in CO2React, produce inert lithium carbonate impurity, these
Remaining lithium impurity can increase charge transfer impedance, and increase polarization, causes the decay of capacity to aggravate.The presence of excessive lithium carbonate is in electricity
The generation of hydrogen fluoride in electrolyte can also be promoted in the cyclic process of pond, positive electrode and collector are caused to corrode.This is also mesh
One technical bottleneck of preceding limitation tertiary cathode material large-scale application at home.
In order to reduce positive electrode residual lithium salt magazine content and reduce its pH value, improve the electrochemistry of positive electrode
Can, people have carried out following research：1st, promote lithium salts volatilization more complete by reducing mixed lithium amount or extending calcination time, so that
The content of the remaining lithium impurity of control；2nd, positive electrode deionized water, bicarbonate, organic acid and various organic solvents are mixed
Processing is dried after being washed and being reacted again；3. coat one layer of thing that can be reacted with lithium salts on positive electrode surface
Matter.In fact, above method all there are problems that, such as reducing mixed lithium amount may cause lithium to lack, so as to cause material to deviate
The stoichiometric ratio of design；The cost of preparation can be then significantly increased by extending calcination time, and have negative shadow to the service life of burner hearth
Ring, be unfavorable for extensive industrialization；Method using washing or organic solvent washing all inevitably makes material
Air and moisture, are very easy to water for the very sensitive tertiary cathode material of environment or carbon dioxide react, body construction
It will be destroyed, chemical property reduces more obvious；Coating mass-energy, which plays material, to be more effectively protected, but generally
Still synthesize using solwution method and tertiary cathode material be modified, however it remains it is mentioned above the problem of.
The content of the invention
It is an object of the invention to provide a kind of tertiary cathode material of surface reaction cladding, possess lithium ion battery excellent
Different chemical property, after multiple charge and discharge cycles, still is able to the higher specific capacity of holding and capacity retention ratio.
Another object of the present invention is to provide a kind of preparation method of the tertiary cathode material of surface reaction cladding, can have
Effect solves the problems, such as generation pollution, corrosive gas during dry grinding, applied widely, gained simple with technique
The composite material arrived has good cyclical stability.
A kind of tertiary cathode material of surface reaction cladding, which is 0.002-0.03 by mass ratio：1 surface
Reaction covering is formed with tertiary cathode material powder technique.
Further, reaction covering in surface is any in boric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium metavanadate
It is one or more of.Generation has faintly acid or middle strong acidity and the chemical combination for being not easy volatilization gas after surface reaction covering heating
Thing, it can react with the remaining lithium of positive electrode particle surface, while the product generated is covered in positive electrode surface,
So that got a promotion by the positive electrode of reaction cladding in the stability of high temperature and room temperature.
Further, tertiary cathode material powder is nickel cobalt aluminic acid lithium powder or nickle cobalt lithium manganate powder.
Further, nickel cobalt aluminic acid lithium powder is Li (Ni0.8Co0.15Al0.05)O2, the nickle cobalt lithium manganate powder is
LiNixCoyMn1-x-yO2, wherein 0.1≤x≤0.9；0.05≤y≤0.9；0.1≤x+y≤0.95.
A kind of preparation method of the tertiary cathode material of above-mentioned surface reaction cladding, comprises the following steps：
Under S1, normal temperature condition, surface reaction covering is placed in milling apparatus with nickel cobalt aluminic acid lithium powder, grinding makes it
Mixture is obtained after mixing.
The mixture, be placed in tube-type atmosphere furnace by S2, heats up and heat preservation sintering obtains primary product.
S3, after the primary product is ground, cross 400 mesh sieves, obtain final product.
Further, reaction covering in surface is any in boric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium metavanadate
It is one or more of.
Further, surface reaction covering and the mass ratio of nickel cobalt aluminic acid lithium powder are 0.002-0.03：1, both are mixed
Close grinding 20-120min.
Further, tube furnace atmosphere furnace is warming up to 250-650 DEG C, and heat preservation sintering 3- with the programming rate of 5 DEG C/min
6h。
Compared with prior art, beneficial effects of the present invention are as follows：
(1) using the technique of dry method cladding, surface reaction coverture occurs anti-the present invention in NCA particle surfaces and remaining lithium
Should, products therefrom is coated on NCA surfaces while consuming remaining lithium, and is prepared eventually through further sintering modified
NCA, surface react coverture and are not likely to produce escaping gas in positive electrode reaction process, environment will not be polluted,
In addition the corrosion resistance for equipment requires relatively low；
(2) addition of the surface reaction covering with extra lithium source is not required in tertiary cathode material reaction process, and
The purpose of protection positive electrode can be played by reacting obtained product；In addition, the height of cladding positive electrode is reacted by surface
Temperature gets a promotion with normal temperature circulation stability；
(3) reaction covering in surface is faintly acid and middle strong acidity, it is greatly reduced after being reacted with tertiary cathode material
Alkali content in positive electrode, can effectively prevent positive electrode exposure in atmosphere there is a phenomenon where the moisture absorption, so as to ensure that just
The stability of pole material, raw material guarantee is provided for subsequent production anode；In addition, after reaction alkaline impurities reduction
Charge transfer impedance can be reduced, reduces polarization, makes the higher specific capacity of battery holding and capacity retention ratio.
Brief description of the drawings
The present invention is further illustrated below in conjunction with the accompanying drawings.
Fig. 1 is scanning electron microscope (SEM) photo of the nickel cobalt lithium aluminate cathode material of the surface reaction cladding in embodiment 11；
Fig. 2 is the nickel cobalt lithium aluminate cathode material of the surface reaction cladding in embodiment 11 and uncoated nickel cobalt lithium aluminate
The chemical property contrast of positive electrode；
Fig. 3 is scanning electron microscope (SEM) photo of the nickel-cobalt lithium manganate cathode material of the surface reaction cladding in embodiment 15；
Fig. 4 is the nickel-cobalt lithium manganate cathode material of the surface reaction cladding in embodiment 15 and uncoated nickle cobalt lithium manganate
The chemical property contrast of positive electrode.
Embodiment
In order to which those skilled in the art are better understood from the present invention, following embodiments make the present invention further detailed
Description.
Embodiment 1
Under S1, normal temperature condition, by boric acid and nickel cobalt aluminic acid lithium powder in mass ratio 0.002:1 is placed in agate mortar or ball milling
In machine, grinding 20min makes it obtain mixture after mixing.
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 250 DEG C with the programming rate of 5 DEG C/min, and keep the temperature
Sintering 6h obtains primary product.
S3, after primary product is ground, cross 400 mesh sieves, obtain final product.
Embodiment 2
Under S1, normal temperature condition, by ammonium dihydrogen phosphate and nickel cobalt aluminic acid lithium powder in mass ratio 0.005:1 is placed in agate mortar
Or in ball mill, grinding 30min makes it obtain mixture after mixing.
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 300 DEG C with the programming rate of 5 DEG C/min, and keep the temperature
Sintering 5.5h obtains primary product.
S3, after primary product is ground, cross 400 mesh sieves, obtain final product.
Embodiment 3
Under S1, normal temperature condition, by diammonium hydrogen phosphate and nickel cobalt aluminic acid lithium powder in mass ratio 0.008:1 is placed in agate mortar
Or in ball mill, grinding 40min makes it obtain mixture after mixing.
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 350 DEG C with the programming rate of 5 DEG C/min, and keep the temperature
Sintering 5h obtains primary product.
S3, after primary product is ground, cross 400 mesh sieves, obtain final product.
Embodiment 4
Under S1, normal temperature condition, by ammonium metavanadate and nickel cobalt aluminic acid lithium powder in mass ratio 0.01:1 be placed in agate mortar or
In ball mill, grinding 50min makes it obtain mixture after mixing.
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 400 DEG C with the programming rate of 5 DEG C/min, and keep the temperature
Sintering 4.5h obtains primary product.
S3, after primary product is ground, cross 400 mesh sieves, obtain final product.
Embodiment 5
Under S1, normal temperature condition, by the mixture of boric acid and ammonium dihydrogen phosphate with nickel cobalt aluminic acid lithium powder in mass ratio
0.014:1 is placed in agate mortar or ball mill, and grinding 60min makes it obtain mixture after mixing.
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 450 DEG C with the programming rate of 5 DEG C/min, and keep the temperature
Sintering 4h obtains primary product.
S3, after primary product is ground, cross 400 mesh sieves, obtain final product.
Embodiment 6
Under S1, normal temperature condition, by the mixture of boric acid and ammonium metavanadate and nickel cobalt aluminic acid lithium powder in mass ratio 0.02:1
It is placed in agate mortar or ball mill, grinding 70min makes it obtain mixture after mixing.
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 550 DEG C with the programming rate of 5 DEG C/min, and keep the temperature
Sintering 3.2h obtains primary product.
S3, after primary product is ground, cross 400 mesh sieves, obtain final product.
Embodiment 7
Under S1, normal temperature condition, the mixture of ammonium dihydrogen phosphate and diammonium hydrogen phosphate and nickel cobalt aluminic acid lithium powder are pressed into quality
Than 0.022:1 is placed in agate mortar or ball mill, and grinding 70min makes it obtain mixture after mixing.
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 550 DEG C with the programming rate of 5 DEG C/min, and keep the temperature
Sintering 3.2h obtains primary product.
S3, after primary product is ground, cross 400 mesh sieves, obtain final product.
Embodiment 8
Under S1, normal temperature condition, by the mixture of diammonium hydrogen phosphate and ammonium metavanadate with nickel cobalt aluminic acid lithium powder in mass ratio
0.024:1 is placed in agate mortar or ball mill, and grinding 90min makes it obtain mixture after mixing.
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 650 DEG C with the programming rate of 5 DEG C/min, and keep the temperature
Sintering 3h obtains primary product.
S3, after primary product is ground, cross 400 mesh sieves, obtain final product.
Embodiment 9
Under S1, normal temperature condition, the mixture of boric acid, ammonium dihydrogen phosphate and ammonium metavanadate and nickel cobalt aluminic acid lithium powder are pressed
Mass ratio 0.028:1 is placed in agate mortar or ball mill, and grinding 110min makes it obtain mixture after mixing.
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 650 DEG C with the programming rate of 5 DEG C/min, and keep the temperature
Sintering 3h obtains primary product.
S3, after primary product is ground, cross 400 mesh sieves, obtain final product.
Embodiment 10
Under S1, normal temperature condition, by boric acid and nickel cobalt aluminic acid lithium powder in mass ratio 0.03:1 is placed in agate mortar or ball milling
In machine, grinding 120min makes it obtain mixture after mixing.
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 650 DEG C with the programming rate of 5 DEG C/min, and keep the temperature
Sintering 3h obtains primary product.
S3, after primary product is ground, cross 400 mesh sieves, obtain final product.
Embodiment 11
0.0927g boric acid particles are weighed under S1, room temperature, 9.608g nickel cobalt lithium aluminate nickel cobalt aluminic acid lithium powders is weighed, is placed in
In agate mortar or ball mill, 30min is ground, it is uniformly mixed and obtains mixture；
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 400 DEG C, and keep the temperature 5h and obtain primary product；
S3, after primary product is ground, cross 400 mesh sieves, modified final product obtained, labeled as NCA-1.
Embodiment 12
0.0921g diammonium hydrogen phosphate particles are weighed under S1, room temperature, weigh 9.604g nickel cobalt lithium aluminate tertiary cathode materials,
It is placed in agate mortar or ball mill, grinds 30min, is uniformly mixed it and obtains mixture；
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 400 DEG C, and keep the temperature 5h and obtain primary product；
S3, after primary product is ground, cross 400 mesh sieves, modified final product obtained, labeled as NCA-2.
Embodiment 13
0.0932g meta-aluminic acid ammonium particles are weighed under S1, room temperature, 9.613g nickel cobalt lithium aluminate tertiary cathode materials is weighed, puts
In agate mortar or ball mill, 30min is ground, it is uniformly mixed and obtains mixture；
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 400 DEG C, and keep the temperature 5h and obtain primary product；
S3, after primary product is ground, cross 400 mesh sieves, modified final product obtained, labeled as NCA-3.
Embodiment 14
0.0929g diammonium hydrogen phosphate particles are weighed under S1, room temperature, weigh 9.620g nickel cobalt lithium aluminate tertiary cathode materials,
It is placed in agate mortar or ball mill, grinds 30min, is uniformly mixed it and obtains mixture；
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 400 DEG C, and keep the temperature 5h and obtain primary product；
S3, after primary product is ground, cross 400 mesh sieves, modified final product obtained, labeled as NCA-4.
Embodiment 15
0.0924g boric acid particles are weighed under S1, room temperature, 9.617g nickle cobalt lithium manganate tertiary cathode materials is weighed, is placed in agate
In Nao mortars or ball mill, 30min is ground, it is uniformly mixed and obtains mixture；
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 400 DEG C, and keep the temperature 5h and obtain primary product；
S3, after primary product is ground, cross 400 mesh sieves, modified final product obtained, labeled as NCM811-1.
Embodiment 16
0.0935g diammonium hydrogen phosphate particles are weighed under S1, room temperature, weigh 9.631g nickle cobalt lithium manganate tertiary cathode materials,
It is placed in agate mortar or ball mill, grinds 30min, is uniformly mixed it and obtains mixture；
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 400 DEG C, and keep the temperature 5h and obtain primary product；
S3, after primary product is ground, cross 400 mesh sieves, modified final product obtained, labeled as NCM811-2.
Embodiment 17
0.0914g meta-aluminic acid ammonium particles are weighed under S1, room temperature, 9.593g nickle cobalt lithium manganate tertiary cathode materials is weighed, puts
In agate mortar or ball mill, 30min is ground, it is uniformly mixed and obtains mixture；
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 400 DEG C, and keep the temperature 5h and obtain primary product；
S3, after primary product is ground, cross 400 mesh sieves, modified final product obtained, labeled as NCM811-3.
Embodiment 18
0.0939g ammonium dihydrogen phosphates are weighed under S1, room temperature, 9.651g nickle cobalt lithium manganate tertiary cathode materials is weighed, is placed in
In agate mortar or ball mill, 30min is ground, it is uniformly mixed and obtains mixture；
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 400 DEG C, and keep the temperature 5h and obtain primary product；
S3, after primary product is ground, cross 400 mesh sieves, modified final product obtained, labeled as NCM811-4.
Comparative example 1
0.0919g ammonium fluoride particles are weighed under S1, room temperature, 9.634g nickel cobalt lithium aluminate tertiary cathode materials is weighed, is placed in
In agate mortar or ball mill, 30min is ground, it is uniformly mixed and obtains mixture；
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 400 DEG C, and keep the temperature 5h and obtain primary product；
S3, after primary product is ground, cross 400 mesh sieves, modified final product obtained, labeled as NCA-F1.
Comparative example 2
0.1348g ammonium fluoride particles are weighed under S1, room temperature, 10.2149g nickle cobalt lithium manganate tertiary cathode materials is weighed, puts
In agate mortar or ball mill, 30min is ground, it is uniformly mixed and obtains mixture；
The mixture, be placed in tube-type atmosphere furnace by S2, is warming up to 400 DEG C, and keep the temperature 5h and obtain primary product；
S3, after primary product is ground, cross 400 mesh sieves, modified final product obtained, labeled as NCM811-F1.
PVDF is dissolved in NMP, the PVDF solution that mass fraction is 3.5% is prepared, stirs evenly and be placed in 80 in baking oven
It is spare after DEG C dry 12h.By NCA-1, the NCA raw material of not any processing and NCM811-1, the NCM811 of not any processing it is former
Material is respectively with conductive black SuperP and above-mentioned PVDF solution according to mass ratio 87：7：6 mixing, after being sufficiently stirred, that is, prepare
Obtain required anode sizing agent.
The preparation of electrode is coated in above-mentioned slurry on 9 microns thick of the bright aluminium foil as collector, treats that NMP is evaporated completely
Quan Hou, electrode slice is rolled with roll squeezer, then is punched into the electrode slice of required diameter, small in 105 DEG C of dryings 12 in vacuum drying oven
When, it is transferred quickly in glove box.Using lithium metal as to electrode, Celgard 2400 is membrane, and electrolyte is containing 2%VC (carbon
Sour vinylene) 1mol/L LiPF6, solvent is EC/DMC/EMC (volume ratios 1:1:1) CR2032 types button electricity, is assembled
Pond.The electrochemistry of constant current charge-discharge test anode material of lithium battery is carried out using the new prestige BTS-5V50mA discharge and recharges instrument in Shenzhen
Energy.
Cycle performance curve is tested：Under the conditions of 25 DEG C, voltage range is 2.8~24.3V (vs Li+/ Li) under to battery
Carry out constant current charge-discharge test and high rate performance test.
The testing procedure of surface pH value is as follows：Under room temperature, 5g NCA positive electrodes powder and 5g NCM811 are disperseed respectively
In 100mL deionized water solutions, measured after stirring 30min using the pH meter of calibration, three are measured using Duplicate Samples
It is secondary, it is averaged.
Refer to Fig. 1 and Fig. 3, nickel cobalt lithium aluminate cathode material and nickel-cobalt lithium manganate cathode material be for spherical form,
After coated, there are coarse particles in its surface, it is known that surface reaction covering respectively with nickel cobalt lithium aluminate cathode material, nickel cobalt manganese
Sour lithium anode material, which reacts and produces, is distributed more uniform clad.
Fig. 2 and Fig. 4 are refer to, 100 circulations of battery made of the NCA-1 materials in embodiment 11 after coated processing
Capacity retention ratio is 96% afterwards, and capacity retention ratio is only 86% after 100 circulations of battery made of uncoated material Pristine；
Capacity retention ratio is 95% after 100 circulations of battery made of NCM811-1 materials in embodiment 15 after coated processing,
Capacity retention ratio is only 86% after 100 circulations of battery made of uncoated material NCM811-1.It can thus be concluded that surface reaction bag
Battery made of the nickel-cobalt lithium manganate cathode material of the nickel cobalt lithium aluminate cathode material covered and surface reaction cladding is respectively provided with higher
Specific discharge capacity.
In conclusion reaction covering in surface provided by the invention can occur instead under given conditions with tertiary cathode material
Should, and uniform clad can be generated in tertiary cathode material particle surface, the tertiary cathode material of coated processing with not into
The tertiary cathode material of row cladding compares the capacity retention ratio with higher, so as to have preferable market application value.
Surface p H test results show that uncoated material NCA surface pH values are 12.6, the material NCA-1 after coating modification
Surface pH value is 11.4；Uncoated material NCM811 surface pH values are 12.4, the material NCM811-1 surface ps H after coating modification
It is worth for 11.3.Thus, the pH of positive electrode can effectively be reduced by reacting covering and tertiary cathode material reaction by surface
It is worth, the alkali content in tertiary cathode material reduces, and the problem of positive electrode exposes the moisture absorption in atmosphere is effectively alleviated, after being easy to
The making of continuous electrode slurry.
Following table discharge capacity and 100 first for the pH value measure of embodiment 11-18 and comparative example 1-2 and under the conditions of 2C
The data statistic of capacity retention ratio after secondary circulation time circulation：
| Base material | React covering in surface | PH value | 2C discharge capacities first | 100 capacity retention ratios of 2C |
| NCA | Boric acid | 11.4 | 157 | 96% |
| NCA | Diammonium hydrogen phosphate | 11.2 | 159 | 95% |
| NCA | Ammonium metavanadate | 11.6 | 162 | 93% |
| NCA | Ammonium dihydrogen phosphate | 11.5 | 155 | 94% |
| NCM811 | Boric acid | 11.3 | 159 | 94% |
| NCM811 | Diammonium hydrogen phosphate | 11.1 | 155 | 93% |
| NCM811 | Ammonium metavanadate | 11.5 | 156 | 91% |
| NCM811 | Ammonium dihydrogen phosphate | 11.3 | 157 | 93% |
| NCA | Ammonium fluoride | 11.2 | 155 | 85% |
| NCM811 | Ammonium fluoride | 11.5 | 154 | 83% |
NCA, NCM811 material in tertiary cathode material reacts covering with a variety of surfaces provided in the present invention respectively
Boric acid, ammonium dihydrogen phosphate, meta-aluminic acid ammonium and diammonium hydrogen phosphate are reacted under given conditions, and respectively obtain corresponding cladding
Positive electrode, in addition in comparative example 1 and comparative example 2 to carry out reacting under mixing same as the previously described embodiments and sintering condition
The decent material of cladding arrived.The data provided by upper table can obtain, NCA-F1 and NCM811-F1 in comparative example, its pH value measured
With the pH of NCA-1, NCA-2, NCA-3, NCA-4, NCM811-1, NCM811-2, NCM811-3 and NCM811-4 in embodiment
Be worth it is close, but its capacity retention ratio relative to each embodiment provide by cladding processing material capacity conservation rate it is low, by
This visible reaction covering in surface provided by the invention has more preferable application value when handling tertiary cathode material.Except this it
Outside, ammonium fluoride easy to absorb moisture itself and hydrogen fluoride and ammonia are easily decomposed to, not only environment are polluted, to consersion unit
Corrosion resistance is more demanding.
The above, is only presently preferred embodiments of the present invention, is not intended to limit the invention, patent protection model of the invention
Enclose and be subject to claims, the equivalent structure change that every description with the present invention is made, should all similarly include
Within the scope of the present invention.
Claims (8)
1. a kind of tertiary cathode material of surface reaction cladding, it is characterised in that the material is 0.002-0.03 by mass ratio：1
Surface reaction covering formed with tertiary cathode material powder technique.
2. positive electrode according to claim 1, it is characterised in that the surface reaction covering is boric acid, di(2-ethylhexyl)phosphate
Any one or a few in hydrogen ammonium, diammonium hydrogen phosphate, ammonium metavanadate.
3. positive electrode according to claim 1, it is characterised in that the tertiary cathode material powder is nickel cobalt lithium aluminate
Powder or nickle cobalt lithium manganate powder.
4. positive electrode according to claim 3, it is characterised in that the nickel cobalt aluminic acid lithium powder is Li
(Ni0.8Co0.15Al0.05)O2；The nickle cobalt lithium manganate powder is LiNixCoyMn1-x-yO2, wherein 0.1≤x≤0.9；0.05≤y
≤0.9；0.1≤x+y≤0.95.
5. the preparation method of the positive electrode according to claim 1-4 any one, it is characterised in that including following step
Suddenly：
Under S1, normal temperature condition, surface reaction covering is placed in milling apparatus with tertiary cathode material powder, grinding makes it mixed
Mixture is obtained after closing uniformly；
The mixture, be placed in tube-type atmosphere furnace by S2, heats up and heat preservation sintering obtains primary product；
S3, after the primary product is ground, cross 400 mesh sieves, obtain final product.
6. according to the method described in claim 5, it is characterized in that, in the step S1, surface reaction covering and ternary are just
Both pole material powders mixed grinding 20-120min.
7. according to the method described in claim 5, it is characterized in that, in the step S2, tube furnace atmosphere furnace is with 5 DEG C/min's
Programming rate is warming up to 250-650 DEG C, and heat preservation sintering 3-6h.
8. according to the method described in claim 5, it is characterized in that, it is characterised in that：The grinding in the step S1 is set
Standby is agate mortar or ball mill.
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