CN108963202A - A kind of ternary layered positive electrode of high temperature modification and its preparation and application - Google Patents
A kind of ternary layered positive electrode of high temperature modification and its preparation and application Download PDFInfo
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Abstract
The present invention relates to a kind of ternary layered positive electrode of high temperature modification and its preparations and application, solid electrolyte is added in positive electrode matrix in the present invention, solid electrolyte is set to be coated on tertiary cathode material matrix surface, it is subsequently heat-treated, to obtain the ternary layered positive electrode of high temperature modification.The ternary layered positive electrode of the high temperature modification that the present invention is prepared is used as the lithium ion battery prepared when the positive electrode of lithium ion battery good cycle at 55 DEG C of high temperature, and high rate performance is high.And preparation method condition provided by the invention is simple, low to the device requirement of production, has unrivaled advantage compared to other lithium ion anode materials.
Description
Technical field
The present invention relates to cell positive material field, in particular to a kind of ternary layered anode of the high temperature modification of lithium ion battery
Material and preparation method thereof.
Background technique
As lithium ion battery flourishes what New-energy electric vehicle field used, energy density is improved, and uses three
First anode is the only way which must be passed.And as energy density requirement is higher and higher, the Ni content requirement of tertiary cathode is higher and higher, or
Person's charge cutoff voltage is higher and higher, and the stability of material goes through one's facings very much, directly affects the cycle performance of lithium ion battery
And security performance.
The LiNi synthesized with Saft is just had studied early in the laboratory Berkeley of the U.S. in 20020.8Co0.15Al0.05O2It is positive
Pole and graphite are the lithium ion battery chemical property of cathode.It is only damaged the study found that the battery recycles 140 weeks capacity at room temperature
4% is lost, and in 60 DEG C of cycle capacity loss 65%.When recycling at high temperature, the internal resistance of cell is significantly raised, causes in C/2 multiplying power
A part of capacitance loss when circulation.When positive and negative anodes are individually studied, discovery cathode can keep initial capacity substantially, and anode damages
Lose 65%.
In order to improve the stability of its material, domestic and international mechanism has carried out largely tertiary cathode especially high-nickel material
Research, Dong-Ju Lee et al. use Ni3(PO4)2The method of cladding is modified NCA positive electrode, the thickness of clad
Degree is 10-20nm, discovery cladding Ni3(PO4)2Afterwards, cycle performance especially high temperature cyclic performance greatly improves.But due to it
Surface coated is the low compound of ionic conductance, and capacity and high rate performance have loss, reduces the power of lithium ion battery
Characteristic.
Therefore, the high temperature of a kind of high temperature cyclic performance that can be improved lithium ion battery tertiary cathode and high rate performance is needed
Type tertiary cathode material and preparation method are to meet the needs in market and 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: it is added in positive electrode matrix
Solid electrolyte makes solid electrolyte be coated on ternary cathode material of lithium ion battery matrix surface, subsequently heat-treated, thus
To the ternary layered positive electrode of high temperature modification.It is recycled at 55 DEG C of the ternary layered positive electrode high temperature of the high temperature modification that the present invention is prepared
Performance is good, and high rate performance is high.And preparation method condition provided by the invention is simple, low to the device requirement of production, thus complete
At the present invention.
The purpose of the present invention is to provide following aspect:
(1) the ternary layered positive electrode of a kind of high temperature modification, the ternary layered positive electrode of high temperature modification includes positive electrode
Matrix and the coating for being coated on matrix surface；
The positive electrode matrix is by formula Li [Ni(1-x-y)MnxCoy](1-z)MzO2Indicate, wherein M be doping metals sun from
Son；0 < x < 1,0 < y < 1,0 z < 0.5 <；
Wherein, M Co, Ni, Mg, Al, Cu or Zn, preferably Al；
The coating is solid electrolyte, preferably lithium ion solid electrolyte.
(2) preparation method of the ternary layered positive electrode of a kind of high temperature modification, comprising the following steps:
Step 1, the precursor solution of coating is prepared；
Step 2, the solution that step 1 obtains is mixed with positive electrode matrix and removes solvent；
Step 3, product step 2 obtained is heat-treated, and obtains final product.
(3) purposes of the ternary layered positive electrode of high temperature modification according to above-mentioned (1),
The ternary layered positive electrode of high temperature modification is applied to lithium ion battery, the positive electrode as lithium ion battery.
The ternary layered positive electrode of a kind of high temperature modification provided according to the present invention and its preparation and application have beneficial below
Effect:
1) battery of the ternary layered positive electrode preparation of high temperature modification provided by the invention 50 weeks circulation volumes at 55 DEG C are protected
Holdup is not less than 93%, improves the high temperature cyclic performance of positive electrode；High rate performance also greatly improves；
2) preparation method of the ternary layered positive electrode of high temperature modification provided by the invention can control in layered cathode material
Surface forms one layer of uniform glass-ceramic solid electrolyte fast-ionic conductor clad, coating thickness 5-20nm；
3) the preparation method whole operation of the ternary layered positive electrode of high temperature modification provided by the invention is simple, controllability and can
Amplification is strong, easy to industrialized production；
4) the ternary layered positive electrode of high temperature modification provided by the invention solve high temperature circulation difference and high rate capability difference
Two main problems also can be applied to so that material can be applied not only to pure electric automobile (EV) to high rate performance requirement
High plug-in hybrid power (PHEV) and hybrid power (HEV) automotive field, that has widened ternary layered material significantly applies model
It encloses.
Detailed description of the invention
Fig. 1 shows blank Li (Ni0.5Mn0.3Co0.2)0.95Al0.05O2SEM figure；
Fig. 2 shows the SEM of 1 product of embodiment figures；
Fig. 3 shows the TEM figure of 1 product of embodiment；
Fig. 4 shows embodiment 1 and blank Li (Ni0.5Mn0.3Co0.2)0.95Al0.05O2Cyclic curve figure.
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 a kind of ternary layered positive electrode of high temperature modification, the ternary layered positive material of the high temperature modification
Material includes positive electrode matrix and the coating for being coated on matrix surface；
The positive electrode matrix is by formula Li [Ni(1-x-y)MnxCoy](1-z)MZO2It indicates, wherein M is doping metals
Cation, preferably Co, Ni, Mg, Al, Cu or Zn, further preferably Al；
Wherein, 0 < x < 1,0 < y < 1,0 z < 0.5 <, preferably 0.1 < x < 0.8,0.1 < y < 0.8,0.01 < z < 0.3, more preferably
It is 0.3, y 0.2 for x, z is 0.05 or x is 0.2, y 0.2, z 0.05.The coating is solid electrolyte, preferably
For lithium ion solid electrolyte, more preferably Li7La3Zr2O12Or Li7La3Ti2O12；
The amount of the coating is that coat the mass ratio of amount of substance and positive electrode matrix be (0.02~7): 100, preferably
For (0.03~6): 100, more preferably (0.05~5): 100.
Inventors believe that the loss of tertiary cathode material capacity is mainly the spy due to caused by the raising of positive impedance
It is not in latter stage of charging.The raising of impedance is related with the reduction of electrode surface conductivity, conductive carbon positive electrode surface loss with
And the organic matter film of positive electrode surface loses ionic conductivity ability when lithium content is lower, and with battery testing temperature
It increases, especially at high temperature, the reduction of electrode surface conductivity is more obvious.
The inventors discovered that in order to improve electrode surface conductivity fast ion can be coated on tertiary cathode material surface
Conductor compound, i.e. solid electrolyte.
Fast-ionic conductor (fast ionic conductor), also referred to as superionic conductors, are called sometimes and do solid electrolyte,
It is different from general ion conductor most basic feature be within the scope of certain temperature have can be comparable with liquid electrolyte
Ionic conductivity (0.01 Ω cm) and low ionic conductance activation energy (≤0.40eV).
Heretofore described lithium ion solid electrolyte, including Li-La-Ti-O system, Li-La-Zr-O system, titanium phosphate
Aluminium lithium (LATP) system, phosphoric acid germanium aluminium lithium (LAGP) system etc., preferably Li7La3Zr2O12Or Li7La3Ti2O12。
The present invention also provides a kind of preparation methods of the ternary layered positive electrode of high temperature modification, comprising the following steps:
Step 1, the precursor solution of coating is prepared；
Step 2, the solution that step 1 obtains is mixed with positive electrode matrix and removes solvent；
Step 3, product step 2 obtained is heat-treated, and obtains final product.
Step 1, the precursor solution of coating is prepared.
In the present invention, the presoma is the main material to prepare solid electrolyte, and the solid electrolyte is lithium
Ion solid electrolyte, preferably Li7La3Zr2O12Or Li7La3Ti2O12；
The precursor solution further includes organic acid, preferably citric acid,
The precursor solution further includes glycol, preferably ethylene glycol,
The solvent of the precursor solution is methanol, ethyl alcohol, isopropanol, acetonitrile, preferably ethyl alcohol.
In one preferred embodiment, Li is prepared according to stoichiometric ratio7La3Zr2O12(LLZO) presoma is molten
Liquid: by the citric acid (C of certain mass6H8O7), ethylene glycol ((CH2OH)2), lithium nitrate (LiNO3), lanthanum nitrate (La (NO3)36·
H2) and zirconyl nitrate (ZrO (NO O3)2) be dissolved in the ethyl alcohol of certain volume and be diluted to target volume, that is, complete precursor solution
Preparation；
Wherein, the dosage of citric acid is the quality of citric acid: total mass of raw material (citric acid, ethylene glycol, lithium nitrate, nitric acid
The quality sum of lanthanum and zirconyl nitrate)=30%~55%, preferably 35%~50%；
Wherein, the dosage of ethylene glycol is the quality of ethylene glycol: total mass of raw material (citric acid, ethylene glycol, lithium nitrate, nitric acid
The quality sum of lanthanum and zirconyl nitrate)=8%~18%, preferably 10%~15%.
In one preferred embodiment, Li is prepared according to stoichiometric ratio7La3Ti2O12(LLTO) presoma is molten
Liquid: by the citric acid (C of certain mass6H8O7), ethylene glycol ((CH2OH)2), lithium nitrate (LiNO3), lanthanum nitrate (La (NO3)36·
H2O it) is dissolved in the ethyl alcohol of certain volume with isopropyl titanate, then is diluted to target volume, that is, complete the preparation of precursor solution；
Wherein, the dosage of citric acid is the quality of citric acid: total mass of raw material (citric acid, ethylene glycol, lithium nitrate, nitric acid
The quality sum of lanthanum and isopropyl titanate)=30%~50%, preferably 35%~45%；
Wherein, the dosage of ethylene glycol is the quality of ethylene glycol: total mass of raw material (citric acid, ethylene glycol, lithium nitrate, nitric acid
The quality sum of lanthanum and isopropyl titanate)=8%~16%, preferably 10%~15%.
The solid electrolyte Li of garnet structure7La3Zr2O12Chemistry and electrochemical stability with higher simultaneously.
For the solid electrolyte Li of garnet structure7La3Zr2O12Preparation, there are mainly two types of synthetic method, tradition at present
Solid phase method, sol-gal process.
The advantages of sol-gal process is that powder granularity is uniform, and stoichiometry is controllable etc., is closed using more extensive powder
At one of method.
Citric acid is also known as Chinese holly edge acid, chemical name 2- hydroxy propane -1,2,3- tricarboxylic acids.According to the difference of its water content,
It is divided into Citric Acid Mono and anhydrous citric acid.At room temperature, citric acid is semi-transparent clear crystal or white particle or white knot
Crystalline substance powder, it is odorless, taste is extremely sour, it is micro- in wet air to have hygroscopy.Citric acid crystal habit is due to crystallization condition difference
Difference, there is anhydrous citric acid, also there is the citric acid containing the crystallization water.It can be deposited in the form of no hydrate or monohydrate
: when citric acid is crystallized from hot water, generate without hydrate；It is crystallized in cold water, generates monohydrate.When being heated to 78 DEG C
Monohydrate can decompose to obtain no hydrate.At 15 degrees Celsius, citric acid can also dissolve in dehydrated alcohol.
From structure, citric acid is a kind of tricarboxylic acid compounds, and therefore has similar physics with other carboxylic acids
And chemical property.It, which can be decomposed, when being heated to 175 DEG C generates carbon dioxide and water, remaining some white crystals.Citric acid is one
The stronger organic acid of kind, there is 3 H+It can ionize；Heating can resolve into multi-products, react with acid, alkali, glycerol etc..
In the present invention, citric acid is complexing agent, so that the mixture of positive electrode matrix and precursor solution is being evaporated
Colloidal sol is formed during solvent, forms gel after drying.
In the present invention, ethylene glycol and citric acid are combined into macromolecular chain, play the role of complexation of metal ions.
Step 2, the solution that step 1 obtains is mixed with positive electrode matrix and removes solvent；
The mass ratio of solid electrolyte and positive electrode matrix that the presoma generates is 0.02%~7%, preferably
0.03%~6%, more preferably 0.05%~5%, such as 1%, 2%, 3%, 5%.
Described be mixed into is carried out by ultrasound and stir process,
The temperature for removing solvent is 40~60 DEG C, such as 50 DEG C.
In one preferred embodiment, sonic oscillation 30min is used when mixing, so that solute disperses more in a solvent
It is uniform.
The temperature for removing solvent is 40~60 DEG C, removes solvent at a temperature of this.
In a preferred embodiment, the temperature for removing solvent is 50 DEG C.The mode for removing solvent does not limit especially
It is fixed, heating water bath is used in the present invention, atmospheric evaporation falls solvent.
The inventors discovered that heat while stirring, when atmospheric evaporation solvent until distilled-to-dryness.On the one hand can add
Fast evaporation rate, is on the other hand heated evenly product system.
In the present invention, the amount for removing solvent makes mixed system become gel-like end.The inventors discovered that removing solvent
Terminate to gel, the cycle performance and high rate performance of obtained final product are more preferable.
After removing solvent, obtained gel-like product is crushed, powder product is obtained.The grinding mode is unlimited, this hair
It is bright middle using grinding.
Step 3, product step 2 obtained is heat-treated, and obtains final product.
The heat treatment temperature be 150~800 DEG C, the time be 3~for 24 hours, heating rate be 0.5~10 DEG C/min.
The heat treatment includes the heating and heat preservation in two stages, and first stage heating and heat preservation is from room temperature (25 DEG C) with 1 DEG C ﹒
min-1Speed be warming up to 200-500 DEG C, keep the temperature 3-10h at this temperature, be then followed by second stage heating and heat preservation be with
0.5-10 DEG C ﹒ min-1It is warming up to 400-700 DEG C, keeps the temperature 4-10h at this temperature；
The purpose of heat treatment stage by stage is: 200-500 DEG C is taken off water of constitution, 400-700 DEG C formed required for object phase.
The heat treatment is is sintered under oxygen atmosphere, tolerance 5-40L/min.After heat treatment, cooling, by what is obtained
Solid crushes, and crosses 300 meshes to get the ternary layered positive electrode of high temperature modification is arrived.
The present invention also provides the purposes of the ternary layered positive electrode of high temperature modification, which is characterized in that the high temperature modification ternary layers
Shape positive electrode is applied to the positive electrode of lithium ion battery, is formed by lithium ion battery 50 weeks circulation volumes at 55 DEG C of 1C
Conservation rate is not less than 93%.
In the preferred embodiment of the present invention, the tertiary cathode material surface cladding solid electrolyte being prepared mentions really
The high high temperature cyclic performance and high rate performance of material, inventors believe that being because of solid electrolyte (fast-ionic conductor
Close object) it is coated on ternary cathode material of lithium ion battery surface, it has blocked between anode material for lithium-ion batteries and electrolyte
Side reaction increases lithium ion battery ionic conductivity, to improve the high temperature circulation of anode material for lithium-ion batteries
Energy and high rate performance.
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
Weigh citric acid 1.5022g, ethylene glycol 0.4437g, lithium nitrate 0.2875g, lanthanum nitrate 0.7738g, zirconyl nitrate
0.3184g, and be mixed and be dissolved in ethyl alcohol 150mL, it is transferred in 250mL volumetric flask, and add ethyl alcohol to solution and be
Li is made in 250mL7La3Zr2O12(LLZO) precursor solution is labeled as LLZO precursor ethanol solution -1；
Weigh 3.00g tertiary cathode material Li (Ni0.5Mn0.3Co0.2)0.95Al0.05O2It is added in 100mL conical flask, so
The LLZO precursor ethanol solution -1 that above-mentioned 30.0mL is added afterwards (is scaled the matter of solid electrolyte LLZO Yu positive electrode matrix
Amount is than being 2wt.%, i.e., LLZO covering amount is 2wt.%), and ethyl alcohol 20mL is added, then carry out at sonic oscillation and stirring
Reason, so that well dispersed in positive electrode matrix ethanol solution；By the suspension of obtained positive electrode in 50 DEG C of heating water baths
Stirring, solvent evaporated ethyl alcohol, until gel terminates；Then gel-like product is smashed and ground, obtains powder product；
Obtained powder product is placed in Muffle furnace, in oxygen atmosphere, air-flow 40mL/min, then from room temperature
(25 DEG C) are with 1 DEG C ﹒ min-1Speed be warming up to 200 DEG C, keep the temperature 3h, then with 1 DEG C ﹒ min-1400 DEG C are warming up to, 4h is kept the temperature, furnace is cold
Afterwards, solid is ground, crosses 300 meshes to get LLZO/Li (Ni is arrived0.5Mn0.3Co0.2)0.95Al0.05O2High temperature modification is compound just
Pole material.
Embodiment 2
Weigh citric acid 7.514g, ethylene glycol 2.2072g, lithium nitrate 0.6141g, lanthanum nitrate 3.8537g, isopropyl titanate
5.32g, and be mixed and be dissolved in ethyl alcohol 150mL, it is transferred in 250mL volumetric flask, and adding ethyl alcohol to solution is 250mL,
Li is made7La3Ti2O12(LLTO) precursor solution is labeled as LLTO precursor ethanol solution -1；
Weigh 3.00g tertiary cathode material Li (Ni0.5Mn0.3Co0.2)0.95Al0.05O2It is added in 100mL conical flask, so
The LLTO precursor ethanol solution -1 that above-mentioned 5.0mL is added afterwards (is scaled the mass ratio of solid electrolyte Yu positive electrode matrix
For 2wt.%, i.e. covering amount is 2wt.%), and ethyl alcohol 20mL is added, sonic oscillation and stir process are then carried out, so that just
It is well dispersed in the material matrix ethanol solution of pole；The suspension of obtained positive electrode is stirred in 50 DEG C of heating water baths, is evaporated
Etoh solvent, until gel terminates；Then gel-like product is smashed and ground, obtains powder product；
Obtained powder product is placed in Muffle furnace, in oxygen atmosphere, air-flow 40mL/min, then from room temperature
(25 DEG C) are with 1 DEG C ﹒ min-1Speed be warming up to 200 DEG C, keep the temperature 3h, then with 1 DEG C ﹒ min-1400 DEG C are warming up to, 4h is kept the temperature, furnace is cold
Afterwards, solid is ground, crosses 300 meshes to get LLTO/Li (Ni is arrived0.5Mn0.3Co0.2)0.95Al0.05O2High temperature modification is compound just
Pole material.
Embodiment 3
Weigh citric acid 1.5022g, ethylene glycol 0.4437g, lithium nitrate 0.2875g, lanthanum nitrate 0.7738g, zirconyl nitrate
0.3184g, and be mixed and be dissolved in ethyl alcohol 150mL, it is transferred in 250mL volumetric flask, and add ethyl alcohol to solution and be
Li is made in 250mL7La3Zr2O12(LLZO) precursor solution is labeled as LLZO precursor ethanol solution -1；
Weigh 3.00g tertiary cathode material Li (Ni0.5Mn0.3Co0.2)0.95Al0.05O2It is added in 100mL conical flask, so
The LLZO precursor ethanol solution -1 of above-mentioned 45mL is added afterwards, and (mass ratio for being scaled solid electrolyte and positive electrode matrix is
3wt.%, i.e. covering amount are 3wt.%), and ethyl alcohol 20mL is added, sonic oscillation and stir process are then carried out, so that positive
It is well dispersed in material matrix ethanol solution；The suspension of obtained positive electrode is stirred in 50 DEG C of heating water baths, is evaporated molten
Agent ethyl alcohol, until gel terminates；Then gel-like product is smashed and ground, obtains powder product；
Obtained powder product is placed in Muffle furnace, in oxygen atmosphere, air-flow 40mL/min, then from room temperature
(25 DEG C) are with 1 DEG C ﹒ min-1Speed be warming up to 200 DEG C, keep the temperature 3h, then with 3 DEG C ﹒ min-1600 DEG C are warming up to, 4h is kept the temperature, furnace is cold
Afterwards, solid is ground, crosses 300 meshes to get LLZO/Li (Ni is arrived0.5Mn0.3Co0.2)0.95Al0.05O2High temperature modification is compound just
Pole material.
Embodiment 4
Weigh citric acid 7.514g, ethylene glycol 2.2072g, lithium nitrate 0.6141g, lanthanum nitrate 3.8537g, isopropyl titanate
5.32g, and be mixed and be dissolved in ethyl alcohol 150mL, it is transferred in 250mL volumetric flask, and adding ethyl alcohol to solution is 250mL,
Li is made7La3Ti2O12(LLTO) precursor solution is labeled as LLTO precursor ethanol solution -1；
Weigh 3.00g tertiary cathode material Li (Ni0.6Mn0.2Co0.2)0.95Al0.05O2It is added in 100mL conical flask, so
The LLTO precursor ethanol solution -1 that above-mentioned 7.5mL is added afterwards (is scaled the mass ratio of solid electrolyte Yu positive electrode matrix
For 3wt.%, i.e. covering amount is 3wt.%), and ethyl alcohol 20mL is added, sonic oscillation and stir process are then carried out, so that just
It is well dispersed in the material matrix ethanol solution of pole；The suspension of obtained positive electrode is stirred in 50 DEG C of heating water baths, is evaporated
Etoh solvent, until gel terminates；Then gel-like product is smashed and ground, obtains powder product；
Obtained powder product is placed in Muffle furnace, in oxygen atmosphere, air-flow 40mL/min, then from room temperature
(25 DEG C) are with 1 DEG C ﹒ min-1Speed be warming up to 200 DEG C, keep the temperature 3h, then with 5 DEG C ﹒ min-1550 DEG C are warming up to, 4h is kept the temperature, furnace is cold
Afterwards, solid is ground, crosses 300 meshes to get LLTO/Li (Ni is arrived0.6Mn0.2Co0.2)0.95Al0.05O2High temperature modification is compound just
Pole material.
Embodiment 5
Weigh citric acid 7.514g, ethylene glycol 2.2072g, lithium nitrate 0.6141g, lanthanum nitrate 3.8537g, isopropyl titanate
5.32g, and be mixed and be dissolved in ethyl alcohol 150mL, it is transferred in 250mL volumetric flask, and adding ethyl alcohol to solution is 250mL,
Li is made7La3Ti2O12(LLTO) precursor solution is labeled as LLTO precursor ethanol solution -1；
Weigh 3.00g tertiary cathode material Li (Ni0.6Mn0.2Co0.2)0.95Al0.05O2It is added in 100mL conical flask, so
The LLTO precursor ethanol solution -1 that above-mentioned 12.5mL is added afterwards (is scaled the mass ratio of solid electrolyte Yu positive electrode matrix
For 5wt.%, i.e. covering amount is 5wt.%), and ethyl alcohol 20mL is added, sonic oscillation and stir process are then carried out, so that just
It is well dispersed in the material matrix ethanol solution of pole；The suspension of obtained positive electrode is stirred in 50 DEG C of heating water baths, is evaporated
Etoh solvent, until gel terminates；Then gel-like product is smashed and ground, obtains powder product；
Obtained powder product is placed in Muffle furnace, in oxygen atmosphere, air-flow 40mL/min, then from room temperature
(25 DEG C) are with 1 DEG C ﹒ min-1Speed be warming up to 200 DEG C, keep the temperature 3h, then with 5 DEG C ﹒ min-1650 DEG C are warming up to, 4h is kept the temperature, furnace is cold
Afterwards, solid is ground, crosses 300 meshes to get LLTO/Li (Ni is arrived0.6Mn0.2Co0.2)0.95Al0.05O2High temperature modification is compound just
Pole material.
Embodiment 6
Weigh citric acid 1.5022g, ethylene glycol 0.4437g, lithium nitrate 0.2875g, lanthanum nitrate 0.7738g, zirconyl nitrate
0.3184g, and be mixed and be dissolved in ethyl alcohol 150mL, it is transferred in 250mL volumetric flask, and add ethyl alcohol to solution and be
Li is made in 250mL7La3Zr2O12(LLZO) precursor solution is labeled as LLZO precursor ethanol solution -1；
Weigh 3.00g tertiary cathode material Li (Ni0.6Mn0.2Co0.2)0.95Al0.05O2It is added in 100mL conical flask, so
The LLZO precursor ethanol solution -1 of above-mentioned 75mL is added afterwards, and (mass ratio for being scaled solid electrolyte and positive electrode matrix is
5wt.%, i.e. covering amount are 5wt.%), and ethyl alcohol 20mL is added, sonic oscillation and stir process are then carried out, so that positive
It is well dispersed in material matrix ethanol solution；The suspension of obtained positive electrode is stirred in 50 DEG C of heating water baths, is evaporated molten
Agent ethyl alcohol, until gel terminates；Then gel-like product is smashed and ground, obtains powder product；
Obtained powder product is placed in Muffle furnace, in oxygen atmosphere, air-flow 40mL/min, then from room temperature
(25 DEG C) are with 1 DEG C ﹒ min-1Speed be warming up to 200 DEG C, keep the temperature 3h, then with 5 DEG C ﹒ min-1650 DEG C are warming up to, 4h is kept the temperature, furnace is cold
Afterwards, solid is ground, crosses 300 meshes to get LLZO/Li (Ni is arrived0.6Mn0.2Co0.2)0.95Al0.05O2High temperature modification is compound just
Pole material.
Comparative example
Comparative example 1
Weigh citric acid 1.5022g, ethylene glycol 0.4437g, lithium nitrate 0.2875g, lanthanum nitrate 0.7738g, zirconyl nitrate
0.3184g, and be mixed and be dissolved in ethyl alcohol 150mL, it is transferred in 250mL volumetric flask, and add ethyl alcohol to solution and be
Li is made in 250mL7La3Zr2O12(LLZO) precursor solution is labeled as LLZO precursor ethanol solution -1；
Weigh 3.00g tertiary cathode material LiNi0.5Mn0.3Co0.2O2It is added in 100mL conical flask, is then added above-mentioned
30.0mL LLZO precursor ethanol solution -1 (mass ratio for being scaled solid electrolyte and positive electrode matrix is 2wt.%,
I.e. covering amount is 2wt.%), and ethyl alcohol 20mL is added, sonic oscillation and stir process are then carried out, so that positive electrode base
It is well dispersed in body ethanol solution；The suspension of obtained positive electrode is stirred in 50 DEG C of heating water baths, solvent evaporated ethyl alcohol,
Terminate to gel；Then gel-like product is smashed and ground, obtains powder product；
Obtained powder product is placed in Muffle furnace, in oxygen atmosphere, air-flow 40mL/min, then from room temperature
(25 DEG C) are with 1 DEG C ﹒ min-1Speed be warming up to 200 DEG C, keep the temperature 3h, then with 1 DEG C ﹒ min-1400 DEG C are warming up to, 4h is kept the temperature, furnace is cold
Afterwards, solid is ground, crosses 300 meshes to get LLZO/LiNi is arrived0.5Mn0.3Co0.2O2Composite positive pole.
Comparative example 2
Weigh citric acid 7.514g, ethylene glycol 2.2072g, lithium nitrate 0.6141g, lanthanum nitrate 3.8537g, isopropyl titanate
5.32g, and be mixed and be dissolved in ethyl alcohol 150mL, it is transferred in 250mL volumetric flask, and adding ethyl alcohol to solution is 250mL,
Li is made7La3Ti2O12(LLTO) precursor solution is labeled as LLTO precursor ethanol solution -1；
Weigh 3.00g tertiary cathode material LiNi0.6Mn0.2Co0.2O2It is added in 100mL conical flask, is then added above-mentioned
(mass ratio for being scaled solid electrolyte and positive electrode matrix is 3wt.% to the LLTO precursor ethanol solution -1 of 7.5mL, i.e.,
Covering amount is 3wt.%), and ethyl alcohol 20mL is added, sonic oscillation and stir process are then carried out, so that positive electrode matrix
It is well dispersed in ethanol solution；The suspension of obtained positive electrode is stirred in 50 DEG C of heating water baths, solvent evaporated ethyl alcohol, until
Gel terminates；Then gel-like product is smashed and ground, obtains powder product；
Obtained powder product is placed in Muffle furnace, in oxygen atmosphere, air-flow 40mL/min, then from room temperature
(25 DEG C) are with 1 DEG C ﹒ min-1Speed be warming up to 200 DEG C, keep the temperature 3h, then with 5 DEG C ﹒ min-1550 DEG C are warming up to, 4h is kept the temperature, furnace is cold
Afterwards, solid is ground, crosses 300 meshes to get LLTO/LiNi is arrived0.6Mn0.2Co0.2O2Composite positive pole.
Comparative example 3
Weigh 3g nickel phosphate Ni3(PO4)2, and be mixed and be dissolved in ethyl alcohol 150mL, it is transferred in 250mL volumetric flask, and
Adding ethyl alcohol to solution is 250mL, and phosphoric acid nickel solution is made；
Weigh 3.00g tertiary cathode material Li (Ni0.5Mn0.3Co0.2)0.95Al0.05O2It is added in 100mL conical flask, so
The nickel phosphate ethanol solution of above-mentioned 7.5mL is added afterwards, and (mass ratio for being scaled solid electrolyte and positive electrode matrix is
3wt.%, i.e. covering amount are 3wt.%), and ethyl alcohol 20mL is added, sonic oscillation and stir process are then carried out, so that positive
It is well dispersed in material matrix ethanol solution；The suspension of obtained positive electrode is stirred in 50 DEG C of heating water baths, is evaporated molten
Agent ethyl alcohol, until gel terminates；Then gel-like product is smashed and ground, obtains powder product；
Obtained powder product is placed in Muffle furnace, in oxygen atmosphere, air-flow 40mL/min, then from room temperature
(25 DEG C) are with 1 DEG C ﹒ min-1Speed be warming up to 200 DEG C, keep the temperature 3h, then with 3 DEG C ﹒ min-1600 DEG C are warming up to, 4h is kept the temperature, furnace is cold
Afterwards, solid is ground, crosses 300 meshes to get Ni is arrived3(PO4)2/Li(Ni0.5Mn0.3Co0.2)0.95Al0.05O2Anode composite
Material.
Comparative example 4
Weigh citric acid 7.514g, ethylene glycol 2.2072g, lithium nitrate 0.6141g, lanthanum nitrate 3.8537g, isopropyl titanate
5.32g, and be mixed and be dissolved in ethyl alcohol 150mL, it is transferred in 250mL volumetric flask, and adding ethyl alcohol to solution is 250mL,
Li is made0.3La0.56TiO3Precursor solution, be labeled as precursor ethanol solution -2；
Weigh 3.00g tertiary cathode material Li (Ni0.6Mn0.2Co0.2)0.95Al0.05O2It is added in 100mL conical flask, so
The precursor ethanol solution -2 of above-mentioned 7.5mL is added afterwards, and (mass ratio for being scaled solid electrolyte and positive electrode matrix is
3wt.%, i.e. covering amount are 3wt.%), and ethyl alcohol 20mL is added, sonic oscillation and stir process are then carried out, so that positive
It is well dispersed in material matrix ethanol solution；The suspension of obtained positive electrode is stirred in 50 DEG C of heating water baths, is evaporated molten
Agent ethyl alcohol, until gel terminates；Then gel-like product is smashed and ground, obtains powder product；
Obtained powder product is placed in Muffle furnace, in oxygen atmosphere, air-flow 40mL/min, then from room temperature
(25 DEG C) are with 1 DEG C ﹒ min-1Speed be warming up to 200 DEG C, keep the temperature 3h, then with 5 DEG C ﹒ min-1550 DEG C are warming up to, 4h is kept the temperature, furnace is cold
Afterwards, solid is ground, crosses 300 meshes to get Li is arrived0.3La0.56TiO3/Li(Ni0.6Mn0.2Co0.2)0.95Al0.05O2It is compound
Positive electrode.
Comparative example 5
Weigh the Li of 3.00g7La3Zr2O12(LLZO) it is dissolved in ethyl alcohol 150mL, and quantitative molten to 250mL ethyl alcohol with volumetric flask
Liquid is labeled as LLZO ethanol solution -11；
Weigh 3.00g tertiary cathode material Li (Ni0.5Mn0.3Co0.2)0.95Al0.05O2It is added in 100mL conical flask, so
The LLZO ethanol solution -11 of above-mentioned 30.0mL is added afterwards, and (mass ratio for being scaled solid electrolyte and positive electrode matrix is
2wt.%, i.e. covering amount are 2wt.%), and ethyl alcohol 20mL is added, sonic oscillation and stir process are then carried out, so that positive
It is well dispersed in material matrix ethanol solution；The suspension of obtained positive electrode is stirred in 50 DEG C of heating water baths, is evaporated molten
Agent ethyl alcohol, until gel terminates；Then gel-like product is smashed and ground, obtains powder product；
Obtained powder product is placed in Muffle furnace, in oxygen atmosphere, air-flow 40mL/min, then from room temperature
(25 DEG C) are with 1 DEG C ﹒ min-1Speed be warming up to 200 DEG C, keep the temperature 3h, then with 1 DEG C ﹒ min-1400 DEG C are warming up to, 4h is kept the temperature, furnace is cold
Afterwards, solid is ground, crosses 300 meshes to get LLZO/Li (Ni is arrived0.5Mn0.3Co0.2)0.95Al0.05O2Composite positive pole.
Experimental example
The SEM of 1 material of experimental example schemes and TEM figure
Fig. 1 shows blank ternary material Li (Ni0.5Mn0.3Co0.2)0.95Al0.05O2SEM figure；
Fig. 2 shows the SEM of 1 product of embodiment figures；
Fig. 3 shows the TEM figure of 1 product of embodiment；
Product after the application cladding it can be seen from Fig. 1 comparison diagram 2 and Fig. 3, particle is uniformly and surface becomes smooth cause
Close, not extra impurity generates.
The 1C cycle performance curve of 2 embodiment of experimental example, 1 product and blank ternary material at 55 DEG C
Embodiment 1 and blank ternary material Li (Ni0.5Mn0.3Co0.2)0.95Al0.05O2Cycle performance curve, such as Fig. 4 institute
Show.Wherein,
A shows blank ternary material Li (Ni0.5Mn0.3Co0.2)0.95Al0.05O2Cycle performance curve；
B shows the cycle performance curve of the product of embodiment 1；
Figure 4, it is seen that the cladding product specific discharge capacity of the application still keeps higher, says after 50 circulations
The electric cycle performance of product is more preferable after bright the application cladding.
3 high rate performance of experimental example
The nC/1C multiplying power data of different samples, as shown in table 1.
In table 1, blank NCM523 refers to Li (Ni0.5Mn0.3Co0.2)0.95Al0.05O2, blank NCM622 refers to Li
(Ni0.6Mn0.2Co0.2)0.95Al0.05O2。
The multiplying power and loop-around data of the different samples of table 1
As can be seen from Table 1, the positive electrode cladding LLTO of the application foreign cation after LLZO, the capacity of material, times
Rate and circulation are all improved；
The ternary layered positive electrode of the high temperature modification being prepared through this method, without being bound by any theory, clad
Effectively prevent the material erosion of HF to its surface in cyclic process, it is suppressed that the increase of charge transfer resistance, therefore wrap
Its cycle performance especially high temperature cyclic performance greatly improves after covering；It and is that solid electrolyte is (fast since its is surface coated
Ion conductor compound), still maintain higher capacity and high rate performance.
Preparation method provided by the invention is easy to operate, controllability and can amplification it is strong, it is easy to industrialized production；The present invention
The ternary layered positive electrode of the high temperature modification of offer will possess the incomparable advantage of other materials in lithium-ion-power cell field.
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 ternary layered positive electrode of high temperature modification, which is characterized in that the ternary layered positive electrode of high temperature modification includes just
Pole material matrix and the coating for being coated on matrix surface.
2. the ternary layered positive electrode of high temperature modification according to claim 1, which is characterized in that the positive electrode matrix tool
There is following general formula:
Li[Ni(1-x-y)MnxCoy](1-z)MzO2,
Wherein,
M is doping metals cation；
0 < x < 1,0 < y < 1,0 < z < 0.5.
3. the ternary layered positive electrode of high temperature modification according to claim 2, which is characterized in that M Co, Ni, Mg, Al, Cu
Or Zn, preferably Al.
4. the ternary layered positive electrode of high temperature modification according to claim 1, which is characterized in that the coating is solid electricity
Xie Zhi, preferably lithium ion solid electrolyte.
5. the ternary layered positive electrode of high temperature modification according to claim 4, which is characterized in that
The coating is Li7La3Zr2O12Or Li7La3Ti2O12, and/or
The amount of the coating is that coat the mass ratio of amount of substance and positive electrode matrix be (0.02~7): 100.
6. a kind of preparation method of the ternary layered positive electrode of high temperature modification, which comprises the following steps:
Step 1, the precursor solution of coating is prepared；
Step 2, the solution that step 1 obtains is mixed with positive electrode matrix and removes solvent；
Step 3, product step 2 obtained is heat-treated, and obtains final product.
7. according to the method described in claim 6, it is characterized in that, in step 1,
The presoma is the main material to prepare solid electrolyte, and the solid electrolyte is lithium ion solid electrolyte,
Preferably Li7La3Zr2O12Or Li7La3Ti2O12；
The precursor solution further includes organic acid, preferably citric acid,
The precursor solution further includes glycol, preferably ethylene glycol,
The solvent of the precursor solution is methanol, ethyl alcohol, isopropanol, acetonitrile, preferably ethyl alcohol.
8. according to the method described in claim 6, it is characterized in that, in step 2,
The mass ratio of solid electrolyte and positive electrode matrix that the presoma generates is 0.02%~7%, preferably
0.03%~6%, more preferably 0.05%~5%；
Described be mixed into is carried out by ultrasound and stir process,
The temperature for removing solvent is 40~60 DEG C, such as 50 DEG C.
9. the method according to one of claim 6 to 8, which is characterized in that in step 3,
The heat treatment temperature be 150~800 DEG C, the time be 3~for 24 hours, heating rate be 0.5~10 DEG C/min.
10. the purposes of -5 any ternary layered positive electrodes of high temperature modification according to claim 1, which is characterized in that described
The ternary layered positive electrode of high temperature modification is applied to the positive electrode of lithium ion battery.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244257A (en) * | 2011-06-15 | 2011-11-16 | 清华大学深圳研究生院 | High-temperature manganic acid lithium cathode material and preparation method thereof |
| CN103762352A (en) * | 2014-01-16 | 2014-04-30 | 东莞新能源科技有限公司 | Modified lithium nickel-cobalt-manganese ternary positive electrode material and preparation method thereof |
| US9601761B2 (en) * | 2013-06-24 | 2017-03-21 | Samsung Electronics Co., Ltd. | Composite cathode active material, method of preparing the composite cathode active material, and cathode and lithium battery each including the composite cathode active material |
| CN107039634A (en) * | 2017-05-04 | 2017-08-11 | 北京科技大学 | Composite lithium ion battery anode and flexible lithium battery, solid state lithium battery preparation method |
| CN107394261A (en) * | 2017-07-03 | 2017-11-24 | 清华大学深圳研究生院 | Lithium metal battery inorganic/organic hybrid films solid electrolyte and preparation method thereof |
| CN107546411A (en) * | 2017-08-30 | 2018-01-05 | 清陶（昆山）能源发展有限公司 | A kind of dielectric film and preparation method thereof |
| CN108054378A (en) * | 2017-12-29 | 2018-05-18 | 中国科学院物理研究所 | Lithium battery composite positive pole with nucleocapsid and preparation method thereof |
-
2018
- 2018-05-28 CN CN201810524115.9A patent/CN108963202A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244257A (en) * | 2011-06-15 | 2011-11-16 | 清华大学深圳研究生院 | High-temperature manganic acid lithium cathode material and preparation method thereof |
| US9601761B2 (en) * | 2013-06-24 | 2017-03-21 | Samsung Electronics Co., Ltd. | Composite cathode active material, method of preparing the composite cathode active material, and cathode and lithium battery each including the composite cathode active material |
| CN103762352A (en) * | 2014-01-16 | 2014-04-30 | 东莞新能源科技有限公司 | Modified lithium nickel-cobalt-manganese ternary positive electrode material and preparation method thereof |
| CN107039634A (en) * | 2017-05-04 | 2017-08-11 | 北京科技大学 | Composite lithium ion battery anode and flexible lithium battery, solid state lithium battery preparation method |
| CN107394261A (en) * | 2017-07-03 | 2017-11-24 | 清华大学深圳研究生院 | Lithium metal battery inorganic/organic hybrid films solid electrolyte and preparation method thereof |
| CN107546411A (en) * | 2017-08-30 | 2018-01-05 | 清陶（昆山）能源发展有限公司 | A kind of dielectric film and preparation method thereof |
| CN108054378A (en) * | 2017-12-29 | 2018-05-18 | 中国科学院物理研究所 | Lithium battery composite positive pole with nucleocapsid and preparation method thereof |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109888204A (en) * | 2019-01-17 | 2019-06-14 | 中国科学院宁波材料技术与工程研究所 | A kind of lithium battery composite positive pole and the preparation method and application thereof |
| CN109888208A (en) * | 2019-01-25 | 2019-06-14 | 高点(深圳)科技有限公司 | Anode material for lithium-ion batteries and its preparation method and application |
| CN109904427A (en) * | 2019-03-04 | 2019-06-18 | 浙江众泰汽车制造有限公司 | The nickelic tertiary cathode material and preparation method of a kind of carbuncle type ion conductor cladding and its lithium ion battery being prepared |
| CN110061212A (en) * | 2019-04-17 | 2019-07-26 | 江西理工大学 | The modified nickelic layered cathode material of garnet-type solid electrolyte and preparation method |
| CN110112383A (en) * | 2019-04-17 | 2019-08-09 | 湖北锂诺新能源科技有限公司 | The nickelic tertiary cathode material and preparation method thereof of titanium phosphate aluminium lithium cladding |
| CN110474018A (en) * | 2019-08-26 | 2019-11-19 | 中南大学 | A kind of modified ternary system lithium battery anode and preparation method thereof |
| CN110690435A (en) * | 2019-10-17 | 2020-01-14 | 中南大学 | Fast ion conductor coated high-nickel ternary positive electrode material and preparation method thereof |
| CN112366295A (en) * | 2020-09-04 | 2021-02-12 | 万向一二三股份公司 | Spherical ternary composite cathode material of lithium ion battery and preparation method thereof |
| CN114094108A (en) * | 2022-01-18 | 2022-02-25 | 浙江帕瓦新能源股份有限公司 | Yttrium-copper double-modified high-nickel cathode material and preparation method thereof |
| CN116779871A (en) * | 2023-08-24 | 2023-09-19 | 浙江帕瓦新能源股份有限公司 | Lithium lanthanum zirconate coated and modified cathode material, preparation method thereof and lithium ion battery |
| CN116779871B (en) * | 2023-08-24 | 2023-11-21 | 浙江帕瓦新能源股份有限公司 | Lithium lanthanum zirconate coated and modified cathode material, preparation method thereof and lithium ion battery |
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