CN109546101A - The preparation method and lithium ion battery of nickel cobalt lithium aluminate cathode material - Google Patents
The preparation method and lithium ion battery of nickel cobalt lithium aluminate cathode material Download PDFInfo
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- CN109546101A CN109546101A CN201811216751.1A CN201811216751A CN109546101A CN 109546101 A CN109546101 A CN 109546101A CN 201811216751 A CN201811216751 A CN 201811216751A CN 109546101 A CN109546101 A CN 109546101A
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- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- 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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Abstract
Present invention discloses the preparation methods and lithium ion battery of a kind of nickel cobalt lithium aluminate cathode material, the preparation method of nickel cobalt lithium aluminate cathode material, the following steps are included: by lithium salts and tungsten source according to molar ratio Li:W=(1.8~2.2): (0.9~1.1) is add to deionized water and stirs, and obtains processing solution；Positive electrode at least containing nickel cobalt lithium aluminate is added in processing solution, and is mixed under the first assigned temperature, until deionized water evaporating completely, obtains intermediate product；Intermediate product is dried；Intermediate product after drying is sintered under the second assigned temperature, in oxygen atmosphere, and is cooled to greenhouse, obtains the positive electrode at least containing nickel cobalt lithium aluminate of tungstate lithium cladding.The performances such as the multiplying power, circulation, safety of nickel cobalt lithium aluminate cathode material can be improved in the preparation method of the nickel cobalt lithium aluminate cathode material.
Description
Technical field
The present invention relates to technical field of lithium ion, especially relate to a kind of system of nickel cobalt lithium aluminate cathode material
Preparation Method and lithium ion battery.
Background technique
Lithium ion battery is widely used to the fields such as 3C Product, electric car, energy storage, especially electric car in recent years
Fast development, the requirement to positive electrode is higher and higher, for the target for reaching the longer course continuation mileage of electric car, it is desirable that lithium from
Sub- battery has higher energy density；Tertiary cathode material nickle cobalt lithium manganate or nickel cobalt lithium aluminate have specific capacity height, price
The advantages that moderate, attracts wide attention, it is considered to be one of most promising anode material for lithium-ion batteries, it has also become new energy
Source automobile (especially riding vehicle) the preferred positive electrode of lithium-ion-power cell, also becomes the exploitation of industrial circle at this stage
Emphasis.
Based on the considerations of battery core security performance and service life, current ternary power battery mainly uses 333,442 and 523, and this is several
The relatively low nickle cobalt lithium manganate series material of a Ni content, but due to current plug-in hybrid-power automobile and pure electric vehicle vapour
Requirement of the vehicle to energy density is higher and higher, therefore 622,811 serial nickel-cobalt lithium manganate materials and nickel cobalt aluminic acid lithium material are got over
To be more taken seriously.
Although conventional nickel cobalt aluminic acid lithium material energy density is very high at present, in charge and discharge process, nickel cobalt lithium aluminate
Strong side reaction can occur for positive electrode and electrolyte interface, so that battery impedance increases, chemical property is reduced, and its table
The Li in face2CO3It can decompose and produce gas, cause safety issue than more prominent.
For problem above existing for nickel cobalt lithium aluminate cathode material, academia and industry mainly pass through selection and suitably mix
Miscellaneous element improves the chemical property and security performance of anode material for lithium-ion batteries, such as middle promulgated by the State Council with the modes such as element are coated
Bright patent application CN201410183175.0 discloses a kind of preparation method of the polynary positive pole material of titanium-oxide-coated, passes through
The nickel cobalt lithium aluminate cathode material doped with rare earth element tb, titanium-oxide-coated is synthesized, structural stability, energy density are improved
And cycle performance, but the metal oxide clad has that lithium-ion-conducting is poor, so that the multiplying power of positive electrode
Performance decline；For another example Chinese invention patent application CN201710752144.6 discloses a kind of indium oxide or tin-doped indium oxide cladding
Positive electrode and preparation method thereof, the electron conduction of indium oxide is excellent, improves the cycle performance of material, but the clad
Ionic conductivity is bad, is unfavorable for lithium ion transport, so that the high rate performance of positive electrode declines.
Therefore, the performances such as the multiplying power, circulation, safety of nickel cobalt lithium aluminate cathode material how are improved, and then improve lithium ion
The performances such as multiplying power, circulation, the safety of battery are those skilled in the art's urgent problems to be solved.
Summary of the invention
The main object of the present invention is to provide the preparation method and lithium ion battery of a kind of nickel cobalt lithium aluminate cathode material, should
The performances such as the multiplying power, circulation, safety of nickel cobalt lithium aluminate cathode material can be improved in the preparation method of nickel cobalt lithium aluminate cathode material.
The present invention proposes a kind of preparation method of nickel cobalt lithium aluminate cathode material, comprising the following steps:
By lithium salts and tungsten source according to molar ratio Li:W=(1.8~2.2): (0.9~1.1) is add to deionized water and stirs
It mixes, obtains processing solution；
Positive electrode at least containing nickel cobalt lithium aluminate is added in processing solution, and is mixed under the first assigned temperature
Stirring, until deionized water evaporating completely, obtains intermediate product；
Intermediate product is dried；
Intermediate product after drying is sintered under the second assigned temperature, in oxygen atmosphere, and is cooled to greenhouse, is obtained
The positive electrode at least containing nickel cobalt lithium aluminate coated to tungstate lithium.
Further, by lithium salts and tungsten source according to molar ratio Li:W=(1.8~2.2): (0.9~1.1) be added to from
It further include producing at least to contain nickel cobalt aluminic acid using sol-gal process before the step of in sub- water and stirring, obtain processing solution
The step of positive electrode of lithium, the step include:
Lithium source, the nickel source+source doped chemical M, cobalt source, silicon source of designated ratio are weighed by the amount of substance, and it is mixed to carry out ball milling
It closes, obtains uniform mix powder, wherein the source doped chemical M is the mixture of the compound of cerium and the compound of indium；
Mix powder is added in the aqueous solution containing polyvinyl alcohol or citric acid or maleic acid, and continues to stir,
Keep mix powder evenly dispersed, obtains mixed liquor；
Mixed liquor is subjected to curing process, obtains xerogel；
Xerogel is pre-sintered under third assigned temperature, in inert atmosphere, and is crushed after being cooled to room temperature；
Broken xerogel is heat-treated under the 4th assigned temperature, in oxygen atmosphere, and is cooled to room temperature, is obtained
To the nickel cobalt lithium aluminate cathode material of cerium, indium codope.
Further, the step of mixed liquor being subjected to curing process, obtaining xerogel, comprising:
Mixed liquor is heated to the first temperature, and keeps the temperature the solvent evaporating completely into mixed liquor, obtains wet gel,
In, the first temperature includes 80~90 DEG C；
Wet gel is dried at the second temperature, obtains xerogel, wherein second temperature includes 90~100 DEG C.
Further, lithium source includes any one in lithium carbonate, lithium sulfate, lithium acetate and lithium chloride, the compound of cerium
Including any one in sulfate corresponding to cerium ion, acetate and villaumite, the compound of indium includes corresponding to indium ion
Sulfate, any one in acetate and villaumite, nickel source includes in sulfate corresponding to nickel ion, acetate and villaumite
Any one, cobalt source includes any one in sulfate corresponding to cobalt ions, acetate and villaumite, silicon source include aluminium from
Any one in sulfate corresponding to son, acetate and villaumite.
Further, third assigned temperature includes 600~700 DEG C, and inert atmosphere includes argon atmosphere, the time of pre-sintering
Including 4~5h, the 4th assigned temperature includes 750~850 DEG C, and the time of heat treatment includes 8~15h.
Further, the first assigned temperature includes 80~100 DEG C, and dry temperature includes 100~120 DEG C, when dry
Between include 4~8h, the second assigned temperature includes 500~700 DEG C, and time of sintering includes 5~10h.
Further, the nickel cobalt lithium aluminate cathode material of cerium, indium codope, molecular formula LiNi(1-x-y-z-w)
CoxAlyCezInWO2, wherein 0≤x≤0.15,0≤y≤0.05,0.005≤z≤0.025,0.005≤w≤0.025.
Further, lithium salts includes any one in lithium hydroxide, lithium carbonate and lithium acetate, and tungsten source includes wolframic acid, partially
Any one in ammonium tungstate and ammonium tungstate.
Further, the additive amount of wolfram element is 500~2000ppm in tungsten source.
The present invention also proposes a kind of lithium ion battery, including anode and cathode, and anode is comprising applying nickel cobalt aluminic acid above-mentioned
The preparation method of lithium anode material and the positive electrode obtained.
The beneficial effects of the present invention are:
1, the preparation method of nickel cobalt lithium aluminate cathode material of the invention can be in the surface shape of nickel cobalt lithium aluminate cathode material
At tungstate lithium clad, wherein the tungstate lithium as mixed conductor material is provided simultaneously with electronic conduction ability and ionic conduction energy
Power will not hinder the migration of electronics and ion, lithium ion conduction when solving common metal oxides, phosphate as clad
The poor problem of property, improves the high rate performance of positive electrode；
2, tungstate lithium clad proposed by the present invention can effectively avoid nickel cobalt lithium aluminate cathode material and directly connect with electrolyte
Touching protects internal positive material, improves the cycle performance and storage performance of positive electrode to inhibit side reaction；
3, the preparation method of nickel cobalt lithium aluminate cathode material of the invention is during tungstate lithium coats, tungstate lithium clad
Formation can consume part residual lithium and to reduce the residual lithium amount of finished product positive electrode improve the processability of positive electrode
Can, and tungstate lithium clad can effectively prevent nickel cobalt lithium aluminate cathode material Surface L i2CO3It is exposed, to inhibit Li2CO3
It decomposes and produces gas, improve the security performance and storage performance of positive electrode；
4, the present invention can get the uniform nickel cobalt lithium aluminate cathode material of clad using the method for coating of wet process cladding,
Further improve the cycle performance of positive electrode.
Detailed description of the invention
Fig. 1 is the flow diagram of the preparation method of nickel cobalt lithium aluminate cathode material in one embodiment of the invention；
Fig. 2 is the idiographic flow schematic diagram that the positive electrode at least containing nickel cobalt lithium aluminate is produced using sol-gal process；
Fig. 3 is the high rate performance comparison diagram of the lithium ion battery prepared in the embodiment of the present invention one and comparative example one；
Fig. 4 is the cycle performance comparison diagram of the lithium ion battery prepared in the embodiment of the present invention one and comparative example one；
Fig. 5 is the storage performance comparison diagram of the lithium ion battery prepared in the embodiment of the present invention one and comparative example one；
Fig. 6 is the security performance comparison diagram of the lithium ion battery prepared in the embodiment of the present invention one and comparative example one.
The embodiments will be further described with reference to the accompanying drawings for the realization, the function and the advantages of the object of the present invention.
Specific embodiment
It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not intended to limit the present invention.
Referring to Fig.1, the embodiment of the present invention proposes a kind of preparation method of nickel cobalt lithium aluminate cathode material, including following step
It is rapid:
Step 11, by lithium salts and tungsten source according to molar ratio Li:W=(1.8~2.2): (0.9~1.1) is added to deionization
It in water and stirs, obtains processing solution；
Step 12, the positive electrode at least containing nickel cobalt lithium aluminate is added in processing solution, and in the first specified temperature
Degree is lower to be mixed, and until deionized water evaporating completely, obtains intermediate product；
Step 13, intermediate product is dried；
Step 14, the intermediate product after drying is sintered under the second assigned temperature, in oxygen atmosphere, and be cooled to
Greenhouse obtains the positive electrode at least containing nickel cobalt lithium aluminate of tungstate lithium cladding.
In above-mentioned steps 11, specifically, lithium salts can be any one in lithium hydroxide, lithium carbonate and lithium acetate, tungsten
Source can be any one in wolframic acid, ammonium metatungstate and ammonium tungstate, preferably, in tungsten source the additive amount of wolfram element be 500~
2000ppm, wherein processing solution obtained is tungstate lithium solution.
In above-mentioned steps 12, used positive electrode can be conventional nickel cobalt lithium aluminate cathode material, can also be with
It is the positive electrode at least containing nickel cobalt lithium aluminate being prepared in situ, intermediate product is to contain tungstate lithium clad and nickel cobalt aluminic acid
The positive electrode of lithium, wherein tungstate lithium clad is adhered on the surface of the positive electrode at least containing nickel cobalt lithium aluminate, preferably
Ground, the first assigned temperature can be 80~100 DEG C.
In above-mentioned steps 13, the purpose that intermediate product is dried is to evaporate the liquid remained on intermediate product
Body, preferably, dry temperature can be 100~120 DEG C, the dry time can be 4~8h.
In above-mentioned steps 14, the purpose that intermediate product is sintered is tungstate lithium clad is enable to glue securely
Invest on the surface of the positive electrode at least containing nickel cobalt lithium aluminate that (in step 12, the adherency of tungstate lithium clad is also less
Securely), comprehensive cladding to the positive electrode at least containing nickel cobalt lithium aluminate is realized, to obtain at least containing for tungstate lithium cladding
There is the positive electrode of nickel cobalt lithium aluminate, wherein preferably, the second assigned temperature can be 500~700 DEG C, the time of sintering can be 5
~10h.
The preparation method of the nickel cobalt lithium aluminate cathode material of the embodiment of the present invention has the advantage that
1, the preparation method can form tungstate lithium clad on the surface of the positive electrode at least containing nickel cobalt lithium aluminate,
In, the tungstate lithium as mixed conductor material is provided simultaneously with electronic conduction ability and ionic conductivity, will not hinder electronics and
The migration of ion, lithium-ion-conducting is poor when solving the problems, such as traditional common metal oxides, phosphate as clad,
Improve the high rate performance of positive electrode；
2, the tungstate lithium clad of the embodiment of the present invention wraps the positive electrode at least containing nickel cobalt lithium aluminate comprehensively
It covers, can effectively avoid positive electrode and directly contacted with electrolyte, to inhibit side reaction, protect internal positive material, mention
The high cycle performance and storage performance of positive electrode；
3, during tungstate lithium coats the positive electrode at least containing nickel cobalt lithium aluminate, the formation of tungstate lithium clad
Part residual lithium can be consumed and improve the processing performance of positive electrode to reduce the residual lithium amount of finished product positive electrode, and
Tungstate lithium clad can effectively prevent nickel cobalt lithium aluminate cathode material Surface L i2CO3It is exposed, to inhibit Li2CO3It decomposes and produces
Gas improves the security performance and storage performance of positive electrode；
4, the embodiment of the present invention uses the method for coating of wet process cladding, coats compared to traditional dry method, can get clad
Uniform nickel cobalt lithium aluminate cathode material, further improves the cycle performance of positive electrode.
It referring to Figures 1 and 2, further include producing at least to contain nickel cobalt aluminium using sol-gal process before above-mentioned steps 11
The step of positive electrode of sour lithium, the step include:
Step 101, lithium source, the nickel source+source doped chemical M, cobalt source, silicon source that designated ratio is weighed by the amount of substance, go forward side by side
Row ball milling mixing obtains uniform mix powder, wherein the source doped chemical M is the mixed of the compound of cerium and the compound of indium
Close object；
Step 102, mix powder is added in the aqueous solution containing polyvinyl alcohol or citric acid or maleic acid, and held
Continuous stirring, keeps mix powder evenly dispersed, obtains mixed liquor；
Step 103, mixed liquor is subjected to curing process, obtains xerogel；
Step 104, xerogel is pre-sintered under third assigned temperature, in inert atmosphere, and after being cooled to room temperature
It is broken；
Step 105, broken xerogel is heat-treated under the 4th assigned temperature, in oxygen atmosphere, and cooling
To room temperature, the nickel cobalt lithium aluminate cathode material of cerium, indium codope is obtained.
In above-mentioned steps 101, specifically, lithium source includes but is not limited in lithium carbonate, lithium sulfate, lithium acetate and lithium chloride
Any one, the compound of cerium includes but is not limited to any one in sulfate corresponding to cerium ion, acetate and villaumite
Kind, the compound of indium includes but is not limited to any one in sulfate corresponding to indium ion, acetate and villaumite, nickel source packet
Include but be not limited to any one in sulfate corresponding to nickel ion, acetate and villaumite, cobalt source include but is not limited to cobalt from
Any one in sulfate corresponding to son, acetate and villaumite, silicon source includes but is not limited to sulfuric acid corresponding to aluminium ion
Any one in salt, acetate and villaumite.
In above-mentioned steps 102, mix powder is added to water-soluble containing polyvinyl alcohol or citric acid or maleic acid
After in liquid, hydrolysis, condensation chemical reaction occur for mix powder, to form mixed liquor (i.e. colloidal sol).
In above-mentioned steps 103, specifically, mixed liquor first can be heated to the first temperature, and keep the temperature into mixed liquor
Solvent evaporating completely obtains wet gel, then again dries wet gel at the second temperature, so that xerogel is obtained, preferably,
First temperature can be 80~90 DEG C, and second temperature can be 90~100 DEG C.
In above-mentioned steps 104, preferably, third assigned temperature can be 600~700 DEG C, argon gas is can be used in inert atmosphere
Atmosphere, the time of pre-sintering can be 4~5h.
In above-mentioned steps 105, cerium, indium codope nickel cobalt lithium aluminate cathode material molecular formula be LiNi(1-x-y-z-w)
CoxAlyCezInWO2, wherein 0≤x≤0.15,0≤y≤0.05,0.005≤z≤0.025,0.005≤w≤0.025, wherein
Preferably, the 4th assigned temperature can be 750~850 DEG C, the time of heat treatment can be 8~15h.
In the present embodiment, sol-gal process be it is a kind of by the compound containing high chemical active ingredient by solution, colloidal sol,
Gel and solidify, then it is thermally treated made of oxide or other compound solids method, with traditional solid phase method, co-precipitation
Method is compared, and the embodiment of the present invention produces the nickel cobalt lithium aluminate cathode material of cerium, indium codope by using sol-gal process, not only
It can guarantee being evenly distributed for positive electrode inside each element, and then improve the structural stability of positive electrode, and by nickel
Ce elements and phosphide element are adulterated in cobalt lithium aluminate cathode material, can overcome traditional nickel cobalt lithium aluminate cathode material in the synthesis process
It is easy to appear the unstable problem of cationic mixing, crystal structure, further improves the cycle performance and safety of positive electrode
Performance.
The embodiment of the present invention also proposes a kind of lithium ion battery, including anode and cathode, wherein anode is aforementioned comprising application
Nickel cobalt lithium aluminate cathode material preparation method and the positive electrode that obtains, specifically, which includes kernel and tungsten
Sour lithium clad, tungstate lithium clad are coated on the surface of kernel, and kernel is the nickel cobalt lithium aluminate anode material of cerium, indium codope
Material.
The nickel that the above embodiment of the present invention is proposed with the performance test results of comparative example combined with specific embodiments below
The preparation method and lithium ion battery of cobalt lithium aluminate cathode material are described in more detail.
Embodiment one
It is weighed in the ratio of ion molar ratio Li:Ni:Co:Al:Ce:In=1.1:0.78:0.15:0.05:0.01:0.01
Lithium sulfate, nickel sulfate, cobaltous sulfate, aluminum sulfate, cerous sulfate and indium sulfate are put into batch mixer, ball milling mixing 1h, are obtained uniform
Mix powder；
Mix powder is added in the aqueous solution containing polyvinyl alcohol, 30min is persistently stirred, obtains mixed liquor；
Mixed liquor is heated to 90 DEG C, the solvent evaporating completely into mixed liquor is kept the temperature, obtains wet gel；
Wet gel is dried at 100 DEG C, obtains xerogel；
Xerogel is pre-sintered 4h in 600 DEG C, argon atmosphere, is crushed after cooled to room temperature, and will be broken
Xerogel is heat-treated 12h in 800 DEG C, oxygen atmosphere, and cooled to room temperature obtains the nickel cobalt lithium aluminate of cerium, indium codope
Positive electrode LiNi0.78Co0.15Al0.05Ce0.01In0.01O2；
Lithium carbonate and ammonium tungstate are add to deionized water according to molar ratio Li:W=1.9:1,1h is stirred, is handled
Solution；
By cerium, the nickel cobalt lithium aluminate cathode material LiNi of indium codope0.78Co0.15Al0.05Ce0.01In0.01O2It is added everywhere
Manage solution in, and 90 DEG C at a temperature of be mixed, until deionized water evaporating completely, obtain intermediate product, wherein wolframic acid
The quality of ammonium is the nickel cobalt lithium aluminate cathode material LiNi of cerium, indium codope0.78Co0.15Al0.05Ce0.01In0.01O2Quality
0.138%；
Intermediate product is dried into 4h at 120 DEG C；
Intermediate product after drying is sintered 5h in 700 DEG C, oxygen atmosphere, naturally cools to greenhouse, obtain cerium (Ce),
Indium (In) codope, tungstate lithium (Li2WO4) cladding nickel cobalt lithium aluminate cathode material, be denoted as Modified-NCA.
Embodiment two
Claim in the ratio of ion molar ratio Li:Ni:Co:Al:Ce:In=1.1:0.79:0.15:0.05:0.005:0.005
Lithium acetate, nickel acetate, cobalt acetate, aluminum acetate, cerous acetate and indium acetate is taken to be put into batch mixer, ball milling mixing 1h is obtained uniformly
Mix powder；
Mix powder is added in the aqueous solution containing polyvinyl alcohol, 30min is persistently stirred, obtains mixed liquor；
Mixed liquor is heated to 90 DEG C, the solvent evaporating completely into mixed liquor is kept the temperature, obtains wet gel；
Wet gel is dried at 100 DEG C, obtains xerogel；
Xerogel is pre-sintered 4h in 600 DEG C, argon atmosphere, is crushed after cooled to room temperature, and will be broken
Xerogel is heat-treated 15h in 750 DEG C, oxygen atmosphere, and cooled to room temperature obtains the nickel cobalt lithium aluminate of cerium, indium codope
Positive electrode LiNi0.79Co0.15Al0.05Ce0.005In0.005O2；
Lithium carbonate and wolframic acid are add to deionized water according to molar ratio Li:W=1.95:1,1h is stirred, is handled
Solution；
By cerium, the nickel cobalt lithium aluminate cathode material LiNi of indium codope0.79Co0.15Al0.05Ce0.005In0.005O2It is added everywhere
Manage solution in, and 90 DEG C at a temperature of be mixed, until deionized water evaporating completely, obtain intermediate product, wherein wolframic acid
Quality be cerium, indium codope nickel cobalt lithium aluminate cathode material LiNi0.79Co0.15Al0.05Ce0.005In0.005O2Quality
0.068%；
Intermediate product is dried into 4h at 120 DEG C；
Intermediate product after drying is sintered 7h in 600 DEG C, oxygen atmosphere, naturally cools to greenhouse, obtain cerium (Ce),
Indium (In) codope, tungstate lithium (Li2WO4) cladding nickel cobalt lithium aluminate cathode material.
Embodiment three
Claim in the ratio of ion molar ratio Li:Ni:Co:Al:Ce:In=1.1:0.75:0.15:0.05:0.025:0.025
Lithium chloride, nickel chloride, cobalt chloride, aluminium chloride, cerium chloride and inidum chloride is taken to be put into batch mixer, ball milling mixing 1h is obtained uniformly
Mix powder；
Mix powder is added in the aqueous solution containing polyvinyl alcohol, 30min is persistently stirred, obtains mixed liquor；
Mixed liquor is heated to 90 DEG C, the solvent evaporating completely into mixed liquor is kept the temperature, obtains wet gel；
Wet gel is dried at 100 DEG C, obtains xerogel；
Xerogel is pre-sintered 4h in 600 DEG C, argon atmosphere, is crushed after cooled to room temperature, and will be broken
Xerogel is heat-treated 8h in 850 DEG C, oxygen atmosphere, cooled to room temperature, obtain cerium, indium codope nickel cobalt lithium aluminate just
Pole material LiNi0.75Co0.15Al0.05Ce0.025In0.025O2；
Lithium hydroxide and ammonium metatungstate are add to deionized water according to molar ratio Li:W=2.0:1,1h is stirred, obtains
Processing solution；
By cerium, the nickel cobalt lithium aluminate cathode material LiNi of indium codope0.75Co0.15Al0.05Ce0.025In0.025O2It is added everywhere
Manage solution in, and 90 DEG C at a temperature of be mixed, until deionized water evaporating completely, obtain intermediate product, wherein inclined tungsten
The quality of sour ammonium is the nickel cobalt lithium aluminate cathode material LiNi of cerium, indium codope0.75Co0.15Al0.05Ce0.025In0.025O2Quality
0.270%；
Intermediate product is dried into 4h at 120 DEG C；
Intermediate product after drying is sintered 10h in 500 DEG C, oxygen atmosphere, greenhouse is naturally cooled to, obtains cerium
(Ce), indium (In) codope, tungstate lithium (Li2WO4) cladding nickel cobalt lithium aluminate cathode material.
Comparative example one
Undoped, uncoated nickel cobalt lithium aluminate cathode material is prepared using the method being the same as example 1
LiNi0.8Co0.15Al0.05O2, it is denoted as Bare-NCA, it will appreciated by the skilled person that related preparation process is herein not
It repeats again.
It is respectively anode with Modified-NCA, Bare-NCA, using artificial graphite as cathode, makes the Soft Roll lithium of 3.4Ah
Ion battery carries out multiplying power, circulation, storage, security performance test to soft bag lithium ionic cell, wherein
High rate performance testing process is as follows: it discharges under the multiplying power of 1/3C, 0.5C, 1C, 2C, 3C and 4C respectively, phase
Close data referring to figure 3. with table 1；
Cycle performance testing process is as follows: at room temperature with 1C charging or discharging current at voltage range 2.8-4.2 to flexible package
Lithium ion battery carry out 500 weeks circulation, related data referring to figure 4. with table 2；
Storage performance testing process is as follows: storage condition is that 4.2V completely fills, and stores in 60 DEG C of insulating boxs, surveyed every 15 days
Examination restores capacity and full electricity stores again, related data referring to figure 5. with table 3；
Security performance testing process is as follows: storage condition is that 4.2V completely fills, and stores in 80 DEG C of insulating boxs, surveyed every 1 day
Battery core volume is tried, was completely filled every 7 days 1 time, related data please refers to Fig. 6 and table 4.
Table 1
Table 2
Table 3
Table 4
From the figure 3, it may be seen that the discharge capacitance of Modified-NCA is substantially better than with the raising of discharge-rate
Bare-NCA, specifically, as shown in Table 1, the Bare-NCA of comparative example one is respectively in times of 1/3C, 0.5C, 1C, 2C, 3C and 4C
Discharge under rate, corresponding discharge capacitance is respectively 100.00%, 98.40%, 96.17%, 93.34%,
92.47% and 90.12%, and the Modified-NCA of the embodiment of the present invention one is respectively in 1/3C, 0.5C, 1C, 2C, 3C and 4C
Discharge under multiplying power, corresponding discharge capacitance is respectively 100.00%, 98.81%, 96.89%, 94.97%,
94.00% and 92.60%, therefore, nickel cobalt lithium aluminate cathode material passes through cerium, indium codope, after tungstate lithium coats, lithium-ion electric
The high rate performance in pond has obtained effective promotion.
As shown in Figure 4, with the increase of cycle-index, the discharge capacitance of Modified-NCA is substantially better than
Bare-NCA, specifically, as shown in Table 2, the discharge capacitance after the Bare-NCA of comparative example one is recycled 500 weeks is
89.67%, and the discharge capacitance after the Modified-NCA of the embodiment of the present invention one is recycled 500 weeks is 94.10%, because
This, nickel cobalt lithium aluminate cathode material passes through cerium, indium codope, and after tungstate lithium coats, the cycle performance of lithium ion battery is obtained
It is effective to be promoted.
As shown in Figure 5, with the extension of storage time, the capacity retention ratio of Modified-NCA is substantially better than Bare-
NCA, specifically, as shown in Table 3, the capacity retention ratio after the Bare-NCA of comparative example one is stored 75 days is 91.33%, and this hair
Capacity retention ratio after the Modified-NCA of bright embodiment one is stored 75 days is 94.28%, therefore, nickel cobalt lithium aluminate anode material
Material passes through cerium, indium codope, and after tungstate lithium coats, the storage performance of lithium ion battery has obtained effective promotion.
It will be appreciated from fig. 6 that the cubical expansivity of Modified-NCA is significantly lower than Bare- with the extension of storage time
NCA, specifically, as shown in Table 4, the cubical expansivity after the Bare-NCA of comparative example one is stored 12 days is 55.69%, and this hair
Cubical expansivity after the Modified-NCA of bright embodiment one is stored 12 days is only 29.32%, therefore, nickel cobalt lithium aluminate anode
Material passes through cerium, indium codope, and after tungstate lithium coats, the security performance of lithium ion battery has obtained effective promotion.
The above description is only a preferred embodiment of the present invention, is not intended to limit the scope of the invention, all utilizations
Equivalent structure or equivalent flow shift made by description of the invention and accompanying drawing content is applied directly or indirectly in other correlations
Technical field, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of nickel cobalt lithium aluminate cathode material, which comprises the following steps:
By lithium salts and tungsten source according to molar ratio Li:W=(1.8~2.2): (0.9~1.1) is add to deionized water and stirs,
Obtain processing solution；
Positive electrode at least containing nickel cobalt lithium aluminate is added in the processing solution, and is mixed under the first assigned temperature
Stirring, until the deionized water evaporating completely, obtains intermediate product；
The intermediate product is dried；
Intermediate product after drying is sintered under the second assigned temperature, in oxygen atmosphere, and is cooled to greenhouse, obtains tungsten
The positive electrode at least containing nickel cobalt lithium aluminate of sour lithium cladding.
2. the preparation method of nickel cobalt lithium aluminate cathode material according to claim 1, which is characterized in that it is described by lithium salts and
Tungsten source is according to molar ratio Li:W=(1.8~2.2): (0.9~1.1) is add to deionized water and stirs, and obtains processing solution
The step of before, further include the steps that producing the positive electrode at least containing nickel cobalt lithium aluminate using sol-gal process, should
Step includes:
Lithium source, the nickel source+source doped chemical M, cobalt source, silicon source of designated ratio are weighed by the amount of substance, and carries out ball milling mixing, are obtained
To uniform mix powder, wherein the source the doped chemical M is the mixture of the compound of cerium and the compound of indium；
The mix powder is added in the aqueous solution containing polyvinyl alcohol or citric acid or maleic acid, and continues to stir,
Keep the mix powder evenly dispersed, obtains mixed liquor；
The mixed liquor is subjected to curing process, obtains xerogel；
The xerogel is pre-sintered under third assigned temperature, in inert atmosphere, and is crushed after being cooled to room temperature；
Broken xerogel is heat-treated under the 4th assigned temperature, in oxygen atmosphere, and is cooled to room temperature, is obtained
The nickel cobalt lithium aluminate cathode material of cerium, indium codope.
3. the preparation method of nickel cobalt lithium aluminate cathode material according to claim 2, which is characterized in that described described to mix
Close the step of liquid carries out curing process, obtains xerogel, comprising:
The mixed liquor is heated to the first temperature, and keeps the temperature the solvent evaporating completely into the mixed liquor, obtains wet gel,
Wherein, first temperature includes 80~90 DEG C；
The wet gel is dried at the second temperature, obtains the xerogel, wherein the second temperature includes 90~100
℃。
4. the preparation method of nickel cobalt lithium aluminate cathode material according to claim 2, which is characterized in that the lithium source includes
Any one in lithium carbonate, lithium sulfate, lithium acetate and lithium chloride, the compound of the cerium includes sulfuric acid corresponding to cerium ion
Any one in salt, acetate and villaumite, the compound of the indium includes sulfate corresponding to indium ion, acetate and chlorine
Any one in salt, the nickel source includes any one in sulfate corresponding to nickel ion, acetate and villaumite, described
Cobalt source includes any one in sulfate corresponding to cobalt ions, acetate and villaumite, and source of aluminium includes that aluminium ion institute is right
Any one in sulfate, acetate and the villaumite answered.
5. the preparation method of nickel cobalt lithium aluminate cathode material according to claim 2, which is characterized in that the third is specified
Temperature includes 600~700 DEG C, and the inert atmosphere includes argon atmosphere, and time of the pre-sintering includes 4~5h, and described the
Four assigned temperatures include 750~850 DEG C, and the time of the heat treatment includes 8~15h.
6. the preparation method of nickel cobalt lithium aluminate cathode material according to claim 1, which is characterized in that described first is specified
Temperature includes 80~100 DEG C, and the temperature of the drying includes 100~120 DEG C, and the time of the drying includes 4~8h, and described the
Two assigned temperatures include 500~700 DEG C, and the time of the sintering includes 5~10h.
7. the preparation method of nickel cobalt lithium aluminate cathode material according to any one of claims 2 to 5, which is characterized in that institute
State the nickel cobalt lithium aluminate cathode material of cerium, indium codope, molecular formula LiNi(1-x-y-z-w)CoxAlyCezInWO2, wherein 0≤
X≤0.15,0≤y≤0.05,0.005≤z≤0.025,0.005≤w≤0.025.
8. the preparation method of nickel cobalt lithium aluminate cathode material according to any one of claims 1 to 6, which is characterized in that institute
Stating lithium salts includes any one in lithium hydroxide, lithium carbonate and lithium acetate, and the tungsten source includes wolframic acid, ammonium metatungstate and wolframic acid
Any one in ammonium.
9. the preparation method of nickel cobalt lithium aluminate cathode material according to claim 8, which is characterized in that in the tungsten source
The additive amount of wolfram element is 500~2000ppm.
10. a kind of lithium ion battery, which is characterized in that including anode and cathode, the anode is comprising applying claim 1 to 9
The preparation method of described in any item nickel cobalt lithium aluminate cathode materials and the positive electrode obtained.
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| CN114156448A (en) * | 2021-11-26 | 2022-03-08 | 格林美（无锡）能源材料有限公司 | Layered high-nickel NCA single crystal type ternary positive electrode material and preparation method thereof |
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Application publication date: 20190329 |