CN109192956A - Basic zirconium phosphate lithium fast-ionic conductor coats nickel cobalt lithium aluminate cathode material and preparation method - Google Patents
Basic zirconium phosphate lithium fast-ionic conductor coats nickel cobalt lithium aluminate cathode material and preparation method Download PDFInfo
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- CN109192956A CN109192956A CN201811051772.2A CN201811051772A CN109192956A CN 109192956 A CN109192956 A CN 109192956A CN 201811051772 A CN201811051772 A CN 201811051772A CN 109192956 A CN109192956 A CN 109192956A
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- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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- 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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- H—ELECTRICITY
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- H01M4/00—Electrodes
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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Abstract
Basic zirconium phosphate lithium fast-ionic conductor coats nickel cobalt lithium aluminate cathode material and preparation method, and the quality of the basic zirconium phosphate lithium fast-ionic conductor is 0.1~10wt%, and the basic zirconium phosphate lithium fast-ionic conductor formation is coated on nickel cobalt lithium aluminate with a thickness of the clad of 5~30nm；The spheric granules that the positive electrode is 5~15 μm of partial size.Preparation method is the following steps are included: (1) prepares the solution containing phosphorus source and zirconium source, and addition zirconium source solution, adds phosphorus source solution in organic solvent or water, stirring adds nickel cobalt lithium aluminate, after carrying out heating stirring reaction, it is slowly evaporated, gained powder is put into baking oven drying；(2) it by step (1) resulting powder, is placed in tube furnace, carries out low temperature Fast Sintering.Positive electrode of the present invention has preferable cyclical stability and multiplying power discharging property；The residual lithium in surface and ternary material cyclical stability low problem when conventional cladding can be effectively reduced in the method for the present invention, technical process is at low cost, simple process, is suitable for big industrial production.
Description
Technical field
The present invention relates to a kind of positive electrodes and preparation method thereof, and in particular to a kind of basic zirconium phosphate lithium fast-ionic conductor cladding
Nickel cobalt lithium aluminate cathode material and preparation method.
Background technique
Lithium ion battery is considered as that can be realized one of most promising energy storage circulating system of power battery, has high energy
The advantages that metric density, operating voltage is high, has a safety feature, stablizes low cost, and toxicity is lower.The development of lithium ion battery, for
It solves energy shortage and reduces environmental pollution to be of great significance.Wherein, positive electrode is to determine its lithium ion battery electrochemistry
The key factor of performance, security performance and Costco Wholesale, but the tertiary cathode material for occupying leading market at present can not still expire
The needs of sufficient Development of Electric Vehicles, energy density and power density and cyclical stability etc. still have to be hoisted.And tertiary cathode
Material surface is easy that side reaction occurs and reduces the invertibity of material with electrolyte；Remained on surface is easy to react with electrolyte simultaneously
Generate the bad organic matter of electric conductivity；And ternary material is placed in air, carbon dioxide and water reaction in meeting and air,
Electro-chemical activity is caused to reduce.Contact due to tertiary cathode material with other substances leads to the cyclical stability of ternary material
Lower with high rate performance.Therefore, tertiary cathode also needs to improve, and the main method for improving tertiary cathode material performance at present has surface
Modification, surface cladding, element doping etc. carry out surface cladding to reduce the side reaction of tertiary cathode material He other substances
It is a kind of very simple and effective method, by the better substance of stability, being coated on tertiary cathode material surface reduces ternary
The decaying of positive electrode electro-chemical activity.
Patent CN105406069 A discloses a kind of method of iron manganese phosphate for lithium cladding ternary material, and the method is with anti-bad
Hematic acid cooperation lithium manganese phosphate and ternary material are dried in vacuo after being mixed, and are carrying out 6 ~ 16h of heat preservation sintering after dry,
By the participation of acidic materials during the method cladding, ternary material is oxide, is easy to be corroded by acidic materials, because of the method
Shortcomings, it is also limited to the improvement of ternary material.
CN107230771 A discloses a kind of method of vanadium phosphate cladding ternary material, and the method is by vanadic salts and phosphate
Reducing agent mixes in deionized water, and after being filtered, washed, drying after stirring and ternary material is by 1 ~ 10:100 charge ratio, in height
It is mixed in fast batch mixer, then 200 ~ 400 degree of lower heat preservation sinterings, the ternary coating modification material coated under non-oxygen atmosphere
Material, the method are mixed by solid phase mixing with solid granule, and cladding is uneven, and active force is faint between solid particle, difficult
To reach film forming or uniformly mixing, and the residual lithium in solid phase mixing ternary surface is still present in ternary surface with solid phase, still shadow
The cycle performance of ternary is rung, this method for coating is limited to the cycle performance improvement of ternary, and there is cladding problem of non-uniform.
Patent CN105047864 A discloses a kind of method using lithium zirconate cladding ternary material, and the method utilizes grass
Hydro-thermal reaction generates zirconium oxide clad, then high temperature sintering under the nickel cobalt manganese presoma and tetrabutyl zirconate 180 degree of hydrochlorate preparation,
The cladding substance of lithium zirconate is obtained, the method is liquid phase zirconium source, using tetrabutyl zirconate as cladding substance, because being liquid phase
There is preferable dispersibility relative to solid phase in the solution, therefore can achieve preferable cladding, but the electrochemistry after cladding
It can still need to further increase.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, provide a kind of cladding table
The residual lithium amount in face is low, and specific capacity height and cycle performance are excellent, and has fabulous stability tertiary cathode material；And the material cost
Low, simple process, low energy consumption is suitable for industrial production.
The technical solution adopted by the present invention to solve the technical problems is as follows: a kind of basic zirconium phosphate lithium fast-ionic conductor cladding nickel
Cobalt lithium aluminate cathode material, the quality of the basic zirconium phosphate lithium fast-ionic conductor are 0.1~10wt%, basic zirconium phosphate lithium fast-ionic conductor
Formation is coated on nickel cobalt lithium aluminate with a thickness of the clad of 5~30nm；The positive electrode is spherical of 5~15 μm of partial size
Grain.
The present invention further solves technical solution used by its technical problem: a kind of basic zirconium phosphate lithium fast-ionic conductor packet
Cover the preparation method of nickel cobalt lithium aluminate cathode material, comprising the following steps:
(1) salt containing P elements and zr element is configured to solution respectively, zirconium source solution and phosphorus source solution are formed, organic molten
Zirconium source solution is added in agent or water, adds phosphorus source solution, stirs evenly, adds nickel cobalt lithium aluminate, it is anti-to carry out heating stirring
Ying Hou is slowly evaporated to muddy, then is transferred to baking oven drying to get powder；
(2) powder obtained by step (1) is placed in tube furnace, in an oxidizing atmosphere, is sintered, obtains the fast ion of basic zirconium phosphate lithium
The nickel cobalt lithium aluminate cathode material of conductor cladding.
Preferably, in step (1), the zirconium source and phosphorus source are configured to solution phase, and solution phase solid-to-liquid ratio is 2~5:100.It is molten
The zirconium source of liquid phase and phosphorus source can be very good to form basic zirconium phosphate lithium gel, if directly adding zirconium source solid, then add di(2-ethylhexyl)phosphate
Hydrogen lithium solid, the lithium dihydrogen phosphate solid particles surface that the latter is added into solution will form basic zirconium phosphate or lithium phosphate solid, resistance
The only further dissolution of lithium dihydrogen phosphate cannot form uniform basic zirconium phosphate lithium gel, if the two has all been made into solution, can keep away
Exempt from this problem.
Preferably, in step (1), the solvent for being configured to solution is water, dehydrated alcohol, ethylene glycol, one in methanol
Kind is several；The zirconium source and phosphorus source molar ratio are 1:1.5 ~ 2.
Preferably, in step (1), the mass volume ratio of the nickel cobalt lithium aluminate and organic solvent or water be 1:100~
200；The ratio covered effect is best.
Preferably, in step (1), the temperature of the heating stirring is 70~90 DEG C, and the time is 90~150min.The stirring
Temperature and mixing time, products therefrom effect are best.
Preferably, in step (1), the basic zirconium phosphate lithium is basic zirconium phosphate lithium derivative L iZr2(PO4)3、Li2ZrP2O8One
Kind is several.
Preferably, in step (1), the zirconium source is one or more of zirconium nitrate, zirconyl nitrate or zirconyl chloride；
Phosphorus source is lithium dihydrogen phosphate.
Preferably, in step (1), the evaporated temperature is 70~90 DEG C, and the time is 20 ~ 50min, is evaporated to slimy
Solid-to-liquid ratio is 1:3 ~ 10.
Preferably, in step (1), the organic solvent is in dehydrated alcohol, ethylene glycol, methanol or N-Methyl pyrrolidone
One or more.
Preferably, in step (1), the mass ratio of the basic zirconium phosphate lithium and nickel cobalt lithium aluminate is 0.1~10:100.
Preferably, in step (1), the partial size of the nickel cobalt lithium aluminate is 5~15 μm.
Preferably, in step (1), the temperature of the drying is 70~90 DEG C, and drying time is 0.5 ~ 2h.
Preferably, in step (2), the oxidizing atmosphere refers to the oxygen of ozone atmosphere, air atmosphere or purity >=99.9%
Gas atmosphere.
Preferably, in step (2), the low temperature Fast Sintering refers to: 400 are warming up to the rate of 3~5 DEG C/min~
700 DEG C, it is sintered 0.5~3h, secondary low temperature Fast Sintering, as few as possible allows temperature to change ternary crystal structure, fast low temperature
Sintering can effectively reduce the destruction of nickel cobalt lithium aluminate lattice, maintain the storage lithium performance of ternary layered structure.Control heating rate master
If avoiding causing physical property to reduce because gap is excessive to control the gap of primary particle in second particle.
The molecular formula of nickel cobalt lithium aluminate of the present invention is LiNi0.8Co0.15Al0.05O2。
The principle of the present invention is: basic zirconium phosphate lithium has fabulous as a kind of solid electrolyte with NASICON structure
Stability and excellent lithium ion transport performance, battery material and other nuisances can both be reduced by being coated on ternary surface
The direct contact of matter, and lithium ion transport rate can be improved；The present invention is initially formed positively charged using phosphate and zirconates as matrix
Milk white gel adds negatively charged tertiary cathode material nickel cobalt lithium aluminate, using positive and negative between liquid phase small particles
Charge attraction effect, adherency on the surface of the material, are evaporated by solid phase solvent, are formed on its surface clad, finally by gained powder
Body material, in its Surface Creation basic zirconium phosphate lithium fast-ionic conductor of tertiary cathode material, it is fast to finally obtain basic zirconium phosphate lithium by sintering
The nickel cobalt aluminium acid lithium battery positive electrode of ion conductor cladding.Basic zirconium phosphate lithium fast-ionic conductor is coated on three as solid electrolyte
First material surface improves the cyclical stability of ternary material, together while can preventing positive electrode and electrolyte that side reaction occurs
Shi Zuowei fast-ionic conductor improves its lithium ion transport stability, the i.e. cyclical stability of material.
Beneficial effects of the present invention are as follows:
(1) in the nickel cobalt lithium aluminate cathode material of basic zirconium phosphate lithium fast-ionic conductor cladding of the present invention, basic zirconium phosphate lithium fast-ionic conductor
Form the clad of 2~20nm of thickness, the spheric granules that the positive electrode is 5~15 μm of partial size；
(2) the nickel cobalt lithium aluminate cathode material that basic zirconium phosphate lithium fast-ionic conductor of the present invention coats is assembled into battery, 2.7~
Under 4.3V, 0.1C, the gram volume that discharges for the first time may be up to 207mAh/g；The gram volume that discharges for the first time at 1C may be up to 183.2mAh/
G, after circulation 100 is enclosed, capacity retention ratio may be up to 84.2%；Respectively under the multiplying power of 0.5C, 1C, 2C, 5C, discharge capacity for the first time
Respectively may be up to 192.3mAh/g, 183.2mAh/g, 162.9mAh/g, 146.8mAh/g, illustrate basic zirconium phosphate lithium of the present invention fastly from
The nickel cobalt lithium aluminate cathode material of sub- conductor cladding has preferable cyclical stability and big multiplying power discharging property；
(3) after the method for the present invention first coats basic zirconium phosphate lithium on nickel cobalt lithium aluminate, then secondary low temperature Fast Sintering, it can effectively reduce
The residual lithium amount on the nickel cobalt lithium aluminate surface of basic zirconium phosphate lithium fast-ionic conductor cladding, reduces residual lithium and side reaction occurs for electrolyte, mentions
Its high storage performance；
(4) the method for the present invention is at low cost, simple process, is suitable for big industrial production.
Detailed description of the invention
Fig. 1 is the nickel cobalt lithium aluminate cathode material of 4 gained basic zirconium phosphate lithium fast-ionic conductor of embodiment of the present invention cladding
SEM figure；
Fig. 2 is 4 gained basic zirconium phosphate lithium fast-ionic conductor of embodiment of the present invention cladding nickel cobalt lithium aluminate cathode material and uncoated
TEM figure；
Fig. 3 is the XRD figure of the nickel cobalt lithium aluminate cathode material of 4 gained basic zirconium phosphate lithium fast-ionic conductor of embodiment of the present invention cladding；
Fig. 4 is that capacity circulating of the battery under 1C multiplying power of the embodiment of the present invention 4 and the assembling of uncoated gained positive electrode compares
Figure.
Specific embodiment
The present invention is described in more detail below by specific embodiment, so that better understanding this hair
It is bright, but following embodiments are not intended to limit the scope of the invention.
Nickel cobalt lithium aluminate used in the embodiment of the present invention is purchased from Ningbo Jinhe New Materials Co., Ltd., partial size 5
~15 μm；Chemical reagent used in the embodiment of the present invention is obtained by routine business approach unless otherwise specified.
Embodiment 1
(1) 0.90513g(0.002108287mol is weighed) five water zirconium nitrates (relative molecular mass 429.32), after being dissolved in water
It is transferred in 50ml volumetric flask, adds deionized water constant volume, it is (opposite to weigh 0.32867g (0.003162431mol) lithium dihydrogen phosphate
Molecular mass 103.93), it is transferred to after being dissolved in water in 50ml volumetric flask, adds water constant volume.Zirconium phosphorus matches 2:3, (this conditions of mixture ratios
Under, 1ml zirconium nitrate adds 1ml lithium dihydrogen phosphate to mix, and what is obtained is matching needed for 1wt% basic zirconium phosphate lithium is coated on ternary material
Than, i.e. each 1ml mixing of two kinds of solution coats aequum for 1wt%, and two kinds of each 0.5ml of solution are 0.5wt% cladding aequum,
The rest may be inferred for remaining covering amount, and easy operation after preparation solution, subsequent need take liquor capacity as proportional quantity, letter in this way
Change operation, similarly hereinafter, be not repeated).
(2) nitre zirconium solution 0.5ml described in above-mentioned (1) is taken with pipette, is added in 10ml water, stirs evenly, add
Above-mentioned (1) described lithium dihydrogen phosphate solution 0.5ml is slowly stirred (this covering amount is 0.5wt% cladding).
(3) it takes 0.5g nickel cobalt lithium aluminate to be added in above-mentioned (2) solution, at 90 DEG C, carries out heating stirring and be evaporated 40min
Afterwards, stirring is dry to evaporating, and is directly transferred in tube furnace afterwards, under oxygen atmosphere, with 5 DEG C/min heating rate, is heated to 650 degree of guarantors
Warm 1h obtains the nickel cobalt lithium aluminate cathode material of basic zirconium phosphate lithium fast-ionic conductor cladding.
Embodiment 2
(1) weigh 0.9051g(0.002108mol) five water zirconium nitrates, be transferred to after being dissolved in water in 50ml volumetric flask, add from
Sub- water constant volume weighs 0.3287g (0.00316mol) lithium dihydrogen phosphate, is transferred in 50ml volumetric flask after being dissolved in water, adds water
Constant volume.Phosphorus zirconium molar ratio is 2:3.
(2) nitre zirconium solution 0.5ml described in above-mentioned (1) is taken with pipette, 75ml alcohol is added, stirs evenly, adds
Above-mentioned (1) described lithium dihydrogen phosphate solution 0.5ml, is slowly stirred.
(3) it takes 0.5g nickel cobalt lithium aluminate to be added in above-mentioned (2) solution, at 90 DEG C, is extremely steamed after carrying out heating stirring 1.5h
Then hair shaft is directly transferred in tube furnace, under oxygen atmosphere, with 5 DEG C/min heating rate, be heated to 650 degree of heat preservation 1h, obtain
The nickel cobalt lithium aluminate cathode material of basic zirconium phosphate lithium fast-ionic conductor cladding.
Embodiment 3
(1) weigh 0.9051g(0.002108mol) five water zirconium nitrates, be transferred to after being dissolved in water in 50ml volumetric flask, add from
Sub- water constant volume weighs 0.3287g (0.00316mol) lithium dihydrogen phosphate, is transferred in 50ml volumetric flask after being dissolved in water, adds water
Constant volume.Phosphorus zirconium molar ratio is 2:3.
(2) nitre zirconium solution 0.5ml described in above-mentioned (1) is taken with pipette, is added in 75ml alcohol, stirs evenly, then plus
Enter above-mentioned (1) described lithium dihydrogen phosphate solution 0.5ml, is slowly stirred.
(3) 0.5g nickel cobalt lithium aluminate is taken to be added in above-mentioned (2) solution, at 90 DEG C, after progress heating stirring is evaporated 1.5h,
Slurry to be mixed becomes viscous, and when about 3 ~ 5ml or so, stops stirring, is slowly evaporated solution, then be transferred to oven drying, is transferred to after dry
In tube furnace, with 5 DEG C/min heating rate, under oxygen atmosphere, 650 degree of heat preservation 1h is heated to, the fast ion of basic zirconium phosphate lithium is obtained and leads
The nickel cobalt lithium aluminate cathode material of body cladding.
Embodiment 4
(1) weigh 0.9051g(0.002108mol) five water zirconium nitrates, be transferred to after being dissolved in water in 50ml volumetric flask, add from
Sub- water constant volume weighs 0.3287g (0.00316mol) lithium dihydrogen phosphate, is transferred in 50ml volumetric flask after being dissolved in water, adds water
Constant volume.Phosphorus zirconium molar ratio is 2:3.
(2) nitre zirconium solution 1ml described in above-mentioned (1) is taken with pipette, is added in 75ml alcohol, stirs evenly, add
Above-mentioned (1) described lithium dihydrogen phosphate solution 1ml, is slowly stirred.
(3) 0.5g nickel cobalt lithium aluminate is taken to be added in above-mentioned (2) solution, at 90 DEG C, after progress heating stirring is evaporated 1.5h,
Slurry to be mixed becomes viscous, and when about 3 ~ 5ml or so, stops stirring, is slowly evaporated solution, then be transferred to oven drying, is transferred to after dry
In tube furnace, with 5 DEG C/min heating rate, under oxygen atmosphere, 650 degree of heat preservation 1h is heated to, basic zirconium phosphate lithium fast-ionic conductor is obtained
The nickel cobalt lithium aluminate cathode material of cladding.
SEM shown in example 4 is as shown in Figure 1
Embodiment 5
(1) weigh 0.9051g(0.002108mol) five water zirconium nitrates, be transferred to after being dissolved in water in 50ml volumetric flask, add from
Sub- water constant volume weighs 0.3287g (0.00316mol) lithium dihydrogen phosphate, is transferred in 50ml volumetric flask after being dissolved in water, adds water
Constant volume.Phosphorus zirconium molar ratio is 2:3.
(2) nitre zirconium solution 5ml described in above-mentioned (1) is taken with pipette, is added in 100ml alcohol, stirs evenly, add
Above-mentioned (1) described lithium dihydrogen phosphate solution 5ml, is slowly stirred.
(3) 0.5g nickel cobalt lithium aluminate is taken to be added in above-mentioned (2) solution, at 90 DEG C, after progress heating stirring is evaporated 1.5h,
Slurry to be mixed becomes viscous, and when about 3 ~ 5ml or so, stops stirring, is slowly evaporated solution, then be transferred to oven drying, is transferred to after dry
In tube furnace, with 5 DEG C/min heating rate, under oxygen atmosphere, 650 degree of heat preservation 1h is heated to, basic zirconium phosphate lithium fast-ionic conductor is obtained
The nickel cobalt lithium aluminate cathode material of cladding.
Comparative example 1
Comparative example 1 and the difference of embodiment 4 are only that: the only nickel cobalt lithium aluminate of uncoated processing, i.e., uncoated in step (2)
Nickel cobalt lithium aluminate cathode material.Without step (1) (2) (3), handle, as a comparison case.
The assembling of battery: weighing nickel cobalt lithium aluminate cathode material obtained by 0.08g, be added 0.01g acetylene black make conductive agent and
0.01 g PVDF(Kynoar) make binder, it is applied on aluminium foil positive plate is made after mixing, in vacuum glove box
It is diaphragm, 1mol/L LiPF with Celgard 2300 using metal lithium sheet as cathode6/ EC:DMC(volume ratio 1:1) it is electrolysis
Liquid is assembled into CR2025 button cell.
Uncoated tertiary cathode material is detected, and the battery assembled is in 2.7~4.3 V voltage ranges, and 0.1C times
Under rate, first discharge specific capacity 204.9mAh/g.It is detected, the battery assembled follows in 2.7~4.3 V voltage ranges
Ring 100 encloses capacity retention ratio, and capacity retention ratio is 40.6% after 300 circle circulations.Respectively in the multiplying power of 0.5C, 1C, 2C, 5C
Under, discharge capacity is respectively 195.1mAh/g, 181.6mAh/g, 158.3mAh/g, 135.2mAh/g for the first time.
The nickel cobalt lithium aluminate cathode material of basic zirconium phosphate lithium fast-ionic conductor cladding is assembled into battery, in 2.7~4.3V, 0.1C
Under, the gram volume that discharges for the first time may be up to 207mAh/g；The gram volume that discharges for the first time at 1C may be up to 183.2mAh/g, circulation 100
After circle, capacity retention ratio may be up to 84.2%；Capacity retention ratio is 63.5% after 280 circle circulations；Respectively in 0.5C, 1C, 2C, 5C
Under multiplying power, discharge capacity may be up to 192.3mAh/g, 183.2mAh/g, 162.9mAh/g, 146.8mAh/g respectively for the first time,
To sum up, basic zirconium phosphate lithium fast-ionic conductor can be effectively coated on nickel cobalt lithium aluminate by the method for the present invention, more uncoated
The nickel cobalt lithium aluminate of basic zirconium phosphate lithium fast-ionic conductor effectively increases the circulation conservation rate and big multiplying power discharging property of the material,
And the pioneering solid electrolyte basic zirconium phosphate lithium type is coated on ternary material surface, process is simple, and process is short, easily grasps
Make, is suitable for big industrial production.
Claims (9)
1. basic zirconium phosphate lithium fast-ionic conductor coats nickel cobalt lithium aluminate cathode material, it is characterised in that: the fast ion of basic zirconium phosphate lithium
The quality of conductor is 0.1~10wt%, and the basic zirconium phosphate lithium fast-ionic conductor formation is coated on a thickness of the clad of 5~30nm
On nickel cobalt lithium aluminate；The spheric granules that the positive electrode is 5~15 μm of partial size.
2. a kind of preparation side of basic zirconium phosphate lithium fast-ionic conductor cladding nickel cobalt lithium aluminate cathode material as described in claim 1
Method, which comprises the following steps:
(1) salt containing P elements and zr element is configured to solution respectively, zirconium source solution and phosphorus source solution are formed, organic molten
Zirconium source solution is added in agent or water, stirs evenly, adds phosphorus source solution, be slowly stirred, forms mixed solution；Add nickel cobalt
Lithium aluminate is slowly evaporated to muddy after carrying out heating stirring reaction, then is transferred to baking oven drying to get powder；
(2) powder obtained by step (1) is placed in tube furnace, in an oxidizing atmosphere, is sintered, obtains the fast ion of basic zirconium phosphate lithium
The nickel cobalt lithium aluminate cathode material of conductor cladding.
3. the preparation method of basic zirconium phosphate lithium fast-ionic conductor cladding nickel cobalt lithium aluminate cathode material according to claim 2,
Be characterized in that: in step (1), solution phase is prepared in the zirconium source, and solution solid-to-liquid ratio is 2~5:100；Phosphorus source prepares solution
Phase, the solid-to-liquid ratio of solution are 2~5:100；The solvent for being configured to solution is water, dehydrated alcohol, ethylene glycol, one in methanol
Kind is several；The zirconium source and phosphorus source molar ratio are 1:1.5 ~ 2.
4. according to the preparation side of any basic zirconium phosphate lithium fast-ionic conductor cladding nickel cobalt lithium aluminate cathode material of claim 2-3
Method, it is characterised in that: in step (1), the nickel cobalt lithium aluminate is 1:100~200 with the mass volume ratio of organic solvent or water；
The slimy solid-to-liquid ratio is 1:3 ~ 10.
5. according to the preparation side of any basic zirconium phosphate lithium fast-ionic conductor cladding nickel cobalt lithium aluminate cathode material of claim 2-4
Method, it is characterised in that: in step (1), the heating stirring temperature is 70~90 DEG C, and the time is 90~150min；It is described slow
Evaporated temperature is 70~90 DEG C, and the time is 20~50min；The temperature of the drying is 70~90 DEG C, and the time is 1 ~ 2h.
6. according to the preparation side of any basic zirconium phosphate lithium fast-ionic conductor cladding nickel cobalt lithium aluminate cathode material of claim 2-5
Method, it is characterised in that: in step (1), the zirconium source is one or more of zirconium nitrate, zirconyl nitrate or zirconyl chloride；Institute
Stating phosphorus source is lithium dihydrogen phosphate；The organic solvent is one of dehydrated alcohol, ethylene glycol, methanol or N-Methyl pyrrolidone
Or it is several.
7. according to the preparation side of any basic zirconium phosphate lithium fast-ionic conductor cladding nickel cobalt lithium aluminate cathode material of claim 2-6
Method, it is characterised in that: in step (1): the basic zirconium phosphate lithium is basic zirconium phosphate lithium derivative L iZr2(PO4)3、Li2ZrP2O8One kind
Or it is several.
8. according to the preparation side of any basic zirconium phosphate lithium fast-ionic conductor cladding nickel cobalt lithium aluminate cathode material of claim 2-7
Method, it is characterised in that: in step (2), the tube furnace sintering temperature is 500 ~ 1100 DEG C, and heating rate is 3 ~ 5 DEG C/min；It burns
The knot time is 0.5 ~ 3h.
9. according to the preparation side of any basic zirconium phosphate lithium fast-ionic conductor cladding nickel cobalt lithium aluminate cathode material of claim 2-8
Method, it is characterised in that: in step (2), the oxidizing atmosphere refers to the oxygen of ozone atmosphere, air atmosphere or purity >=99.9%
Gas atmosphere；The basic zirconium phosphate lithium and nickel cobalt lithium aluminate mass ratio are 0.1~10:100.
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| 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 |
| CN110350190A (en) * | 2019-07-01 | 2019-10-18 | 湖北锂诺新能源科技有限公司 | Basic zirconium phosphate lithium surface modification richness lithium rock salt oxide anode material and preparation method thereof |
| CN113716623A (en) * | 2021-08-27 | 2021-11-30 | 中国地质大学（武汉） | High-nickel ternary material LiNi0.80Co0.15Al0.05O2Coating method of |
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| 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 |
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