CN106058240A - Preparation method of high-voltage lithium battery composite with core-shell structure - Google Patents
Preparation method of high-voltage lithium battery composite with core-shell structure Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-voltage lithium battery composite with core-shell structure, cobalt lithium phosphate with high electrochemical stability is used as a shell with nano-scale thickness, and nickel lithium manganate with high electrochemical stability is used as a core. A composite of the cobalt lithium phosphate and nickel lithium manganate gives full play to their respective advantages through their synergy, thereby effectively improving specific capacity, cyclability and high-work-temperature electrochemical properties of the composite. The composite has high energy density, good recyclability and good rate capability, and its preparation process is simple and feasible.
Description
Technical field
The invention belongs to the technical field of new energy materials, be specifically related to the preparation method of lithium battery combination electrode material.
Background technology
Along with going deep into traditional energy crisis cognition, development can replace the novel energy of the traditional energies such as oil coal
Become the most urgent.In recent years, high performance lithium ion battery because having that energy density is big, have extended cycle life, memory-less effect,
The advantages such as volume is little, lightweight, non-environmental-pollution have become as microgrid/off-network power station, energy vehicle, the weight of portable electric appts
Want energy-storage units.Positive electrode is as one of the core of lithium ion battery, and its quality greatly determines lithium ion battery
Performance, the most always people research focus.
Nickel ion doped (LiNi for lithium ion battery0.5Mn1.5O4) material have up to 650Wh/kg energy density,
Low consumption high security, synthesis technique simplicity are prone to the advantages such as industrialization.Nickel ion doped because of its have high voltage, high-energy-density and
It it is considered as the important component part of lithium ion battery electrode material of future generation.But nickel ion doped is at the high voltage platform of 4.7V
Under, due to self John-Teller effect and lattice defect etc., it is easily caused electrolyte decomposition, Mn Ion release and ion
Ducting capacity is poor, and the charge-discharge performance causing material is poor, capacity attenuation and the problem of high rate performance difference.Particularly at height
Under multiplying power and hot conditions, Mn3+Can accelerate to be dissolved in electrolyte and cause capacity sharp-decay, simultaneously the Ni2+ of high-valence state/
Ni4+ also can be dissolved in electrolyte, causes electrode material performance to decline further.Surface coating is to improve nickel ion doped electrochemistry
One of effective way of performance.[Fan Y, Wang J, Tang Z, the et al.Effects of the such as Fan Y
nanostructured SiO2coating on the performance of LiNi0.5Mn1.5O4cathode
materials for high-voltage Li-ion batteries[J].ElectrochimicaActa,2007,52
(11): 3870-3875.] SiO is used2Cladding nickel ion doped material, when covering amount is 1%, after circulation 100 circle, capability retention
Reach 86%, a certain degree of inhibit the HF corrosion to electrode material, but SiO2Substantial amounts of hydroxy functional group can promote again
It reacts with electrolyte, causes the problem of electrolyte decomposition flatulence to produce, and is faced with many difficulties in actual application.China
Patent application CN201510641270.5 discloses the preparation method of a kind of composite cladding nickel ion doped, at pure phase nickel mangaic acid
Lithium presoma suspension adds calcium salt, zirconates, titanium salt composite solution, through filtering, wash, obtaining CaO-ZrO after drying2-TiO2
Cladding nickel ion doped presoma；Calcine the most in air atmosphere and make annealing treatment, obtaining CaO-ZrO2-TiO2Cladding nickel mangaic acid
Lithium composite material.Resulting materials reaches 100 circulation volumes of 130mAh/g, 0.2C multiplying power in 0.2C first discharge specific capacity and keeps
Rate is 97%.[Liu, J.and A.Manthiram, the Improved electrochemical performance such as Liu, J
of the 5V spinel cathode LiMn1.5Ni0.42Zn0.08O4by surface modification[J]
.Journal of The Electrochemical Society, 2009.156 (1): A66-A72] use Al2O3As surface
Decorative material, covering amount is 2%, is prepared for Al2O3Cladding nickel lithium manganate cathode material.Cycle performance be improved significantly, circulation
After 50 circles, capability retention reaches 99%.At present, existing Surface coating material conductivity is poor, is improving cycle performance
Simultaneously, it is impossible to be effectively improved the big high rate performance of material；And covering material belongs to electrochemicaUy inert material mostly, covering amount is too high
Can seriously reduce the specific capacity of material.
Summary of the invention
The goal of the invention of the present invention is to provide a kind of cycle performance and the excellent nickel ion doped composite of high rate performance
Preparation method, this method modifies cladding cobalt phosphate lithium, the nickel mangaic acid after cladding by nickel lithium manganate cathode material carries out surface
Lithium is greatly improved as cell positive material various aspects of performance.
For solving above-mentioned technical problem, the present invention provides the preparation of the high-voltage lithium composite of a kind of nucleocapsid structure
Method, it comprises the steps:
(1) first prepare nickel ion doped material, be fully ground standby；
(2) weigh a certain amount of phosphoric acid and cobalt salt, be dissolved in appropriate solvent, be made into certain density settled solution A；
(3) a certain amount of nickel ion doped material is joined in solution A, after mixing, be sufficiently stirred for and ultrasonic make nickel mangaic acid
Powder for lithium is the most dispersed, is configured to solution B；
(4) weigh a certain amount of lithium salts to be dissolved in appropriate solvent, be slowly dropped in the solution B being stirred continuously；Use ammonia
The pH of water regulation solution B is 5.8-10.0, continuously stirred rear ultrasonic；
(5) solution of step (4) is proceeded to autoclave, react 5-36 hour at 120-300 DEG C, then by hydro-thermal
Product is centrifuged washing and drying, and in last Muffle furnace, sintering obtains the nickel ion doped composite wood of Surface coating cobalt phosphate lithium
Material.
Preferably, the cobalt phosphate lithium of surface coating layer is composite gross mass percentage ratio 1%-10%.
Preferably, in step (2), (4) solvent for use be deionized water, ethanol, acetone one or more；Step (2)
In cobalt salt used be cobaltous acetate, cobalt nitrate, cobaltous sulfate one or more；In step (4), lithium salts used is Lithium hydrate, nitric acid
Lithium, lithium acetate one or more.
Preferably, described in step (4), ammonia concn is 1%-28%, adds ammonia regulation pH5.8-10.0, persistently stirs
Ultrasonic 5-15min after mixing the 5-30min time.
Preferably, in step (5) in Muffle furnace 650 DEG C-750 DEG C sinter 1-15 hour.
Preferably, in above-mentioned reaction, the phosphate of addition, cobalt salt, the molar ratio range value of lithium salts are 1:1:1.5.
Preferably, the preparation method of described step (1) nickel lithium manganate cathode material is coprecipitation: configuration 0.5-2mol/L
Manganese salt, nickel salt solution, use 0.5-2mol/L sodium carbonate liquor as precipitant, at 50 DEG C, coprecipitation reaction 3-10 is little
Time, stir speed (S.S.) 80-200rpm.Separate coprecipitated product, wash repeatedly, be dried.Stoichiometrically weigh lithium salts, with coprecipitated
Shallow lake product is sufficiently mixed.By mixture tabletting, heat 3 hours at 400 DEG C, cool to room temperature with the furnace.Gained pretreatment product grinds
The broken tabletting of pulverizing, reacts 3-10 hour at 900 DEG C, is cooled to 700 DEG C and reacts 6-12 hour.Heat treatment reaction is all empty at normal pressure
Carry out in atmosphere Muffle furnace.Furnace cooling prepares nickel ion doped, grinds standby.
Preferably, the preparation method of described step (1) nickel lithium manganate cathode material is ball-milling method: based on nickel ion doped chemistry
Amount ratio, weighs appropriate lithium salts, manganese salt, nickel salt, is placed in ball grinder ball milling, ball milling 1-12 hour under 60-200rpm rotating speed.Ball milling
Product tabletting, heats 3 hours at 400 DEG C, cools to room temperature with the furnace.Gained pretreatment product grinds tabletting, at 900 DEG C
React 3-10 hour, be cooled to 700 DEG C and react 6-12 hour.Heat treatment reaction is all carried out in atmospheric air atmosphere Muffle furnace.With
Stove cooling prepares nickel ion doped, grinds standby.
Preferably, in the coprecipitation of nickel lithium manganate cathode material or ball-milling method, lithium salts selected from Lithium hydrate, lithium carbonate,
One in lithium acetate, manganese salt one in manganese carbonate, manganese sulfate, manganese nitrate, manganese acetate, nickel salt is selected from nickelous carbonate, sulfur
One in acid nickel, nickel nitrate, nickel acetate.
Preferably, the preparation method of the present invention is the preparation method of 4.7V anode material of lithium battery.
Second aspect present invention provides the high-voltage lithium composite of a kind of nucleocapsid structure, and it is by following preparation method
Obtain:
(1) first prepare nickel ion doped material, be fully ground standby；
(2) weigh a certain amount of phosphoric acid and cobalt salt, be dissolved in appropriate solvent, be made into certain density settled solution A；
(3) a certain amount of nickel ion doped material is joined in solution A, after mixing, be sufficiently stirred for and ultrasonic make nickel mangaic acid
Powder for lithium is the most dispersed, is configured to solution B；
(4) weigh a certain amount of lithium salts to be dissolved in appropriate solvent, be slowly dropped in the solution B being stirred continuously；Use ammonia
The pH of water regulation solution B is 5.8-10.0, continuously stirred rear ultrasonic；
(5) solution of step (4) is proceeded to autoclave, react 5-36 hour at 120-300 DEG C, then by hydro-thermal
Product is centrifuged washing and drying, and in last Muffle furnace, sintering obtains the nickel ion doped composite wood of Surface coating cobalt phosphate lithium
Material.
Preferably, in the high-voltage lithium composite of nucleocapsid structure, the cobalt phosphate lithium of surface coating layer is nanoscale
Thickness, accounts for composite gross mass percentage ratio 1%-10%.
Another aspect of the present invention provides a kind of electrochemical cell, including:
(1) anode,
(2) electrolyte；
(3) negative electrode；Wherein negative electrode is a kind of anode material for lithium-ion batteries system prepared by method described in claim 1
Become；
(4) barrier film.
Cobalt phosphate lithium is also the high-tension positive electrode of 4.7V, and himself theoretical capacity is up to 170mAh/g, with nickel mangaic acid
The compound voltage platform that not only will not reduce entirety of lithium, has certain castering action on the contrary to capacity.But cobalt phosphate lithium is led
The poorest, generally need height nanorize just can have certain electrochemistry capacitance, the advantage of cobalt phosphate lithium is electrochemically stable
Property high, with electrolyte, there is the good compatibility.And nickel ion doped has good conductivity, electrochemistry capacitance and good rate capability
Feature, but electrochemical stability is poor.The present invention prepares the 4.7V high-voltage composite cathode material of a kind of nucleocapsid structure, with electricity
The cobalt phosphate lithium that chemical stability is higher is shell (nanometer grade thickness), and the nickel ion doped that electro-chemical activity is higher is core.C.I. Pigment Violet 14
The composite of lithium and nickel ion doped, by the synergism between its two component, has fully played two kinds of positive electrodes each
Advantage, thus be effectively improved the specific capacity of material, cycle performance and the chemical property under relatively elevated operating temperature thereof.
Advantages of the present invention:
1., it is contemplated that develop the preparation method of high performance 4.7V anode material of lithium battery, this method is at nickel ion doped
Surface cobalt phosphate lithium carry out coating decoration, the mass percent of cobalt phosphate lithium cladding nickel ion doped is 1-10%.After cladding
Composite there is good cycle performance, high rate performance, and the best chemical property；
2. the present invention uses the cobalt phosphate lithium with electro-chemical activity to compare employing inert matter cladding as clad
Layer, the method will not substantially reduce the specific capacity of nickel ion doped, significantly improves cycle performance and the multiplying power of nickel ion doped on the contrary
Performance, further increases the practicality of material.
3. the present invention prepares the 4.7V high-voltage composite cathode material of a kind of nucleocapsid structure, the phosphorus that electrochemical stability is higher
Acid cobalt lithium is shell (nanometer grade thickness), and the nickel ion doped that electro-chemical activity is higher is core.Cobalt phosphate lithium and nickel ion doped compound
Material, by the synergism between its two component, has fully played the respective advantage of two kinds of positive electrodes, thus effectively
Improve the specific capacity of material, cycle performance and the chemical property under relatively elevated operating temperature thereof.
4. the present invention uses hydro-thermal method to carry out Surface coating, and not only cladding is comprehensively, and the most pollution-free, technique letter
Single.
5. the composite positive pole of the present invention accounts for more than the 90% of total capacity at the capacity of 4.7V discharge platform.
Accompanying drawing illustrates:
Figure 1A is embodiment 1,2,3 gained nickel ion doped phase pure material and cobalt phosphate lithium cladding nickel ion doped composite
XRD comparison diagram, the characteristic peak that XRD diffraction maximum is cobalt phosphate lithium of Figure 1B.
Fig. 2 is the scanning electron microscope (SEM) photograph of embodiment 2 gained cobalt phosphate lithium cladding nickel ion doped material, and wherein Fig. 2 A is times magnification
Number is 2000 times, Fig. 2 B is to amplify the Electronic Speculum figure of 31450 times.
Fig. 3 is the scanning electron microscope (SEM) photograph of embodiment 4 resulting materials, and wherein Fig. 3 A is embodiment 4 (1) gained nickel ion doped material
Amplify 20000 times, Fig. 3 B be that embodiment 4 (2) gained cobalt phosphate lithium cladding nickel ion doped material amplifies the Electronic Speculum figure of 30000 times.
Fig. 4 is embodiment 1,2,3 gained nickel ion doped phase pure material and cobalt phosphate lithium cladding nickel ion doped composite
Chemical property curve chart, wherein Fig. 4 A is charging and discharging curve first, and Fig. 4 B is the discharge capacity figure of circulation 100 times.
Detailed description of the invention
The following examples are that the present invention is expanded on further, but present disclosure is not limited to this.Present invention explanation
Embodiment in book is only used for that the present invention will be described, and protection scope of the present invention is not played restriction effect by it.This
The protection domain of invention is only defined by the claims, and those skilled in the art are institute on the basis of embodiment disclosed by the invention
Any omission of making, replace or revise and fall within protection scope of the present invention.
Embodiment 1
(1) preparing nickel ion doped material initially with coprecipitation, preparation process is: by nickel ion doped stoichiometry score
Another name takes nickel sulfate and manganese sulfate, adds after being completely dissolved in 1L deionized water, and solution concentration is 1mol/L.Dripped in 1 hour
Enter the sodium carbonate liquor 1.5L that concentration is 1mol/L, fill into proper ammonia regulation pH value 11-12, by coprecipitated product separation, water
Washing repeatedly to filtrate pH value close to 7, product proceeds to be dried 3 hours at air dry oven 100 DEG C, and dried object is placed on through grinding
Pre-burning product, 400 DEG C, air atmosphere pre-burning 3 hours, is fully ground, at 5MPa pressure lower sheeting, sample strip is put by Muffle furnace
Insulation reaction 6 hours at 900 DEG C in high temperature reaction stove, are cooled to 700 DEG C of also insulation reaction 12 hours, furnace cooling.By institute
Obtaining sample and be fully ground standby, sample XRD test is shown to be nickel ion doped (in accompanying drawing 1 shown in pure sample XRD).
(2) under hydrothermal reaction condition, it is achieved cobalt phosphate lithium is coated with at nickel ion doped particle surface: weigh 3.59g concentration
85% H being3PO4It is the cobaltous acetate of 99.5% with 7.78g purity, fills in 500mL distilled water and 100mL alcohol mixed solution
Divide stirring and dissolving wiring solution-forming A.The nickel ion doped powder body that 500g step (1) prepares, stirring is added in above-mentioned mixed liquor
30min, ultrasonic 10min wiring solution-forming B, then weigh the Lithium hydrate of 5.5g and be dissolved in the distilled water of 80mL and 20mL ethanol mixes
Close in liquid, mix with mixed solution B and continue to stir 20min.The ammonia regulation PH to 7.0 using concentration to be 28%.Proceed to 1L
The hydrothermal reaction kettle of volume carries out hydro-thermal reaction, stir speed (S.S.) 50rpm, reacts 10 hours at temperature is 190 DEG C.Hydro-thermal is anti-
Answer that product is centrifugal, washing repeatedly, dry, tabletting, in Muffle furnace, 700 DEG C sinter 10 hours.Furnace cooling, product divides through element
Analysis test shows that cobalt phosphate lithium covering amount is 1% (mass percent), through XRD test, product shows that product is the most still for nickel mangaic acid
Lithium, cobalt phosphate lithium amount is very few does not shows corresponding diffraction maximum in XRD tests.The cobalt phosphate lithium of gained/nickel ion doped composite
Mix homogeneously with acetylene black, PVDF and be prepared as positive pole after slurrying, with lithium sheet as negative pole, assemble (under argon gas atmosphere) in glove box
Become half-cell, carry out charge-discharge test.
Embodiment 2
Coprecipitation prepares nickel ion doped material with embodiment 1 (1)；
Weighing concentration is the H of 85%3PO43.59g and 7.78g cobaltous acetate, is completely dissolved in 500ml distilled water and 50ml ethanol
Dissolve wiring solution-forming A, be added thereto to 100g nickel ion doped powder body, ultrasonic 10min wiring solution-forming B after stirring 30min, then claim
Amount 5.5g Lithium hydrate is dissolved in distilled water and the 20ml alcohol mixed solution of 80ml, and mixed solution is added drop-wise to mixed solution
In B, continue stirring 20min.With the ammonia regulation PH to 7.0 that concentration is 28%.Final gained mixed liquor is proceeded to 1L volume
Hydrothermal reaction kettle carries out hydro-thermal reaction, stir speed (S.S.) 50rpm, reacts 10 hours at temperature is 190 DEG C.By hydro-thermal reaction product
Centrifugal, washing repeatedly, dry, tabletting, in Muffle furnace, 700 DEG C sinter 10 hours.Furnace cooling, product is tested through elementary analysis
Show that cobalt phosphate lithium covering amount is 2.8% (mass percent).The cobalt phosphate lithium of gained/nickel ion doped composite and acetylene
It is prepared as positive pole after black, PVDF mix homogeneously slurrying, with lithium sheet as negative pole, glove box is assembled into (under argon gas atmosphere) half electricity
Pond, carries out charge-discharge test.
Embodiment 3
Coprecipitation prepares nickel ion doped material with embodiment 1 (1)；
Weighing concentration is the H of 85%3PO43.59g and 7.78g cobaltous acetate, is completely dissolved in 500ml distilled water and 50ml ethanol
Dissolve wiring solution-forming A, be added thereto to 50g nickel ion doped powder body, ultrasonic 10min wiring solution-forming B after stirring 30min, then claim
Amount 5.5g Lithium hydrate is dissolved in distilled water and the 20ml alcohol mixed solution of 80ml, and mixed solution is added drop-wise to mixed solution
In B, continue stirring 20min.With the ammonia regulation PH to 7.0 that concentration is 28%.Final gained mixed liquor is proceeded to 1L volume
Hydrothermal reaction kettle carries out hydro-thermal reaction, stir speed (S.S.) 50rpm, reacts 10 hours at temperature is 190 DEG C.By hydro-thermal reaction product
Centrifugal, washing repeatedly, dry, tabletting, in Muffle furnace, 700 DEG C sinter 10 hours.Furnace cooling, product is tested through elementary analysis
Show that cobalt phosphate lithium covering amount is 6.5% (mass percent).Through XRD test, product shows that product is the most still for nickel ion doped, phosphorus
Acid cobalt lithium shows faint characteristic diffraction peak in XRD tests.The cobalt phosphate lithium of gained/nickel ion doped composite and acetylene
It is prepared as positive pole after black, PVDF mix homogeneously slurrying, with lithium sheet as negative pole, glove box is assembled into (under argon gas atmosphere) half electricity
Pond, carries out charge-discharge test.
Embodiment 4
(1) ball-milling method is used to prepare nickel ion doped material.Preparation process is: by nickel ion doped stoichiometric proportion, weigh carbon
Acid lithium, manganese sulfate, nickel sulfate, reactant gross mass is 50g, is placed in ball grinder ball milling, ball milling 3 hours under 100rpm rotating speed.
Ball milling product tabletting, heats 3 hours at 400 DEG C, cools to room temperature with the furnace.Gained pretreatment product grinds tabletting, 900
React 6 hours at DEG C, be cooled to 700 DEG C and react 10 hours.Furnace cooling prepares nickel ion doped, is fully ground pulverizing standby.Produce
Thing is regular spinel structure (as shown in accompanying drawing 3A schemes).
(2) under hydrothermal reaction condition, it is achieved cobalt phosphate lithium is coated with at nickel ion doped particle surface.Weigh 3.59g concentration
85% H being3PO4It is the cobaltous acetate of 99.5% with 7.78g purity, fills in 500mL distilled water and 100mL alcohol mixed solution
Divide stirring and dissolving wiring solution-forming A.The nickel ion doped powder body that 100g step (1) prepares, stirring is added in above-mentioned mixed liquor
30min, ultrasonic 10min wiring solution-forming B, then weigh the Lithium hydrate of 5.5g and be dissolved in the distilled water of 80mL and 20mL ethanol mixes
Close in liquid, mix with mixed solution B and continue to stir 20min.The ammonia regulation PH to 7.0 using concentration to be 28%.Proceed to 1L
The hydrothermal reaction kettle of volume carries out hydro-thermal reaction, stir speed (S.S.) 50rpm, reacts 10 hours at temperature is 190 DEG C.Hydro-thermal is anti-
Answer that product is centrifugal, washing repeatedly, dry, tabletting, in Muffle furnace, 700 DEG C sinter 10 hours.Furnace cooling, product divides through element
Analysis test shows that cobalt phosphate lithium covering amount is 6.6% (mass percent), and product is still regular spinel structure, but surface has
Significantly cobalt phosphate lithium nano-particle attachment (as shown in accompanying drawing 3B schemes).
The cobalt phosphate lithium of gained/nickel ion doped composite is mixed homogeneously with acetylene black, PVDF and is prepared as positive pole after slurrying,
With lithium sheet as negative pole, in glove box, it is assembled into half-cell (under argon gas atmosphere), carries out charge-discharge test.
Table 1 is the chemical property under above-described embodiment difference test condition
Examples detailed above, only for technology design and the feature of the explanation present invention, its object is to allow the person skilled in the art be
Will appreciate that present disclosure and implement according to this, can not limit the scope of the invention with this.All according to present invention essence
God's equivalent transformation of being done of essence or modification, all should contain within protection scope of the present invention.
Claims (10)
1. the preparation method of the high-voltage lithium composite of a nucleocapsid structure, it is characterised in that it comprises the steps:
(1) first prepare nickel ion doped material, be fully ground standby；
(2) weigh a certain amount of phosphoric acid and cobalt salt, be dissolved in appropriate solvent, be made into certain density settled solution A；
(3) a certain amount of nickel ion doped material is joined in solution A, after mixing, be sufficiently stirred for and ultrasonic make nickel ion doped powder
Body is the most dispersed, is configured to solution B；
(4) weigh a certain amount of lithium salts to be dissolved in appropriate solvent, be slowly dropped in the solution B being stirred continuously；Use ammonia is adjusted
The pH of joint solution B is 5.8-10.0, continuously stirred rear ultrasonic；
(5) solution of step (4) is proceeded to autoclave, react 5-36 hour at 120-300 DEG C, then by hydro-thermal reaction
Product is centrifuged washing and drying, and in last Muffle furnace, sintering obtains the nickel ion doped composite of Surface coating cobalt phosphate lithium.
Preparation method the most according to claim 1, it is characterised in that the cobalt phosphate lithium of surface coating layer is that composite is total
Mass percent 1%-10%.
Preparation method the most according to claim 1, it is characterised in that in step (2), (4) solvent for use be deionized water,
Ethanol, acetone one or more；In step (2) cobalt salt used be cobaltous acetate, cobalt nitrate, cobaltous sulfate one or more；Step
Suddenly in (4) lithium salts used be Lithium hydrate, lithium nitrate, lithium acetate one or more.
Preparation method the most according to claim 1, it is characterised in that described in step (4), ammonia concn is 1%-28%,
Add ammonia regulation pH 5.8-10.0, ultrasonic 5-15min after the continuously stirred 5-30min time.
Preparation method the most according to claim 1, it is characterised in that 650 DEG C-750 DEG C sintering in Muffle furnace in step (5)
1-15 hour.
Preparation method the most according to claim 1, it is characterised in that the phosphoric acid that adds in above-mentioned reaction, cobalt salt, lithium salts
Molar ratio range value is 1:1:1.5.
Preparation method the most according to claim 1, it is characterised in that described preparation method is 4.7V anode material of lithium battery
Preparation method.
8. the high-voltage lithium-battery cathode material of a nucleocapsid structure, it is characterised in that it is obtained by following preparation method:
(1) first prepare nickel ion doped material, be fully ground standby；
(2) weigh a certain amount of phosphoric acid and cobalt salt, be dissolved in appropriate solvent, be made into certain density settled solution A；
(3) a certain amount of nickel ion doped material is joined in solution A, after mixing, be sufficiently stirred for and ultrasonic make nickel ion doped powder
Body is the most dispersed, is configured to solution B；
(4) weigh a certain amount of lithium salts to be dissolved in appropriate solvent, be slowly dropped in the solution B being stirred continuously；Use ammonia is adjusted
The pH of joint solution B is 5.8-10.0, continuously stirred rear ultrasonic；
(5) solution of step (4) is proceeded to autoclave, react 5-36 hour at 120-300 DEG C, then by hydro-thermal reaction
Product is centrifuged washing and drying, and in last Muffle furnace, 650 DEG C-750 DEG C sintering obtain Surface coating cobalt phosphate lithium for 1-15 hour
Nickel ion doped composite.
The high-voltage lithium-battery cathode material of nucleocapsid structure the most according to claim 8, it is characterised in that surface coating layer
Cobalt phosphate lithium be nanometer grade thickness, account for composite gross mass percentage ratio 1%-10%.
10. an electrochemical cell, including:
(1) anode,
(2) electrolyte；
(3) negative electrode；Wherein negative electrode is that a kind of anode material for lithium-ion batteries prepared by method described in claim 1 is made；
(4) barrier film.
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| CN109417165A (en) * | 2016-11-22 | 2019-03-01 | 株式会社Lg化学 | Including core and the positive electrode active materials particle of shell of phosphoric acid cobalt lithium and preparation method thereof containing lithium and cobalt oxides |
| CN109860591A (en) * | 2018-12-12 | 2019-06-07 | 无锡晶石新型能源股份有限公司 | A kind of production technology of lithium manganese phosphate cladding nickel ion doped |
| CN112768643A (en) * | 2019-11-06 | 2021-05-07 | 湖南杉杉能源科技股份有限公司 | Lithium ion battery anode composite material and preparation method thereof |
| TWI818888B (en) * | 2023-05-18 | 2023-10-11 | 台灣中油股份有限公司 | Lithium nickel manganese oxide core shell material and manufacture method thereof |
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