CN109786679A - A kind of lithium ion battery composite cathode material and preparation method thereof - Google Patents
A kind of lithium ion battery composite cathode material and preparation method thereof Download PDFInfo
- Publication number
- CN109786679A CN109786679A CN201711122689.5A CN201711122689A CN109786679A CN 109786679 A CN109786679 A CN 109786679A CN 201711122689 A CN201711122689 A CN 201711122689A CN 109786679 A CN109786679 A CN 109786679A
- Authority
- CN
- China
- Prior art keywords
- magnesium
- solution
- phosphoric acid
- positive pole
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a kind of lithium ion battery composite cathode materials, coat one layer on cobalt acid lithium material matrix surface and mix magnesium phosphoric acid aluminium layer.Preparation method of the invention: ease of solubility aluminium salt and ease of solubility magnesium salts are dissolved in solvent, solution A is obtained；Diffluent phosphorus hydrochlorate is dissolved in solvent, solution B is obtained；Under agitation, solution B is injected into solution A, the pH value for controlling system in reaction process is 4-6, and resulting product is filtered, washed, is dried, and obtains unformed mixing magnesium phosphoric acid alumina particles；It mixes magnesium phosphoric acid alumina particles by unformed and is uniformly mixed with cobalt acid lithium material, sintering is to get arriving composite positive pole.The present invention carries out encapsulated magnesium-doped phosphoric acid aluminium layer to cobalt acid lithium material matrix and modifies, the incorporation of magnesium elements improves the crystallinity of clad, improve the electrolyte resistance erosiveness of composite positive pole, being isolated for electrolyte and active material can be kept under the longer time, and then improves the cycle performance and security performance of lithium ion battery.
Description
Technical field
The invention belongs to cell positive material field more particularly to a kind of lithium ion battery composite cathode material and its preparations
Method.
Background technique
In lithium ion anode material, lithium cobaltate cathode material due to operating voltage with higher, energy density, quickly
It charge and discharge and the advantages such as is easily-synthesized and is widely used.But lithium cobaltate cathode material, after deep charge, high price cobalt ions is easy
It reacts with electrolyte, causes cycle performance to deteriorate, security performance is deteriorated.
To solve the above-mentioned problems, the main method taken at present be matrix is doped and surface cladding.Pass through tune
The stably-doped structure of whole inactive elemental coats layer of material on lithium cobaltate cathode material surface, prevents positive electrode and electricity
The direct contact for solving liquid, reacts with electrolyte to effectively inhibit high price cobalt ions, improves the stability of positive electrode active materials,
Safety and cycle performance.
Current study show that inert to electrolyte in one layer of cobalt acid lithium or other positive active material particle surfaces cladding
Aluminum phosphate, the cycle performance and thermal stability of material can be improved；But exist simultaneously following phenomenon: (1) specific capacity is damaged for the first time
It loses larger；(2) since clad crystallinity is low, erosion resistance is poor, and after recycling for a long time, clad is more easily damaged.
Mainly had using the method for aluminum phosphate clad anode active material in the prior art: one, the aluminum phosphate that will have been prepared
Particle, which is scattered in solvent, is prepared into suspension, and then positive active material particle is added in above-mentioned dispersion suspension, mixing
Uniformly, it then dries, be sintered；Two, aluminum salt solution or salting liquid containing other elements is added in positive active material, being then added can
Soluble phosphoric acid salting liquid makes its surface in situ generate aluminum phosphate clad, is finally heat-treated.But the first above-mentioned side
Method will form reunion when dispersing in a solvent, aluminum phosphate cannot be evenly distributed on because aluminum phosphate is not soluble in water or organic solvent
Positive electrode surface；Second method, the compactness that the uniformity of aluminum phosphate, aluminum phosphate are contacted with the surface of positive electrode active materials
Improved, but acidity is presented in the hydrolysis of ease of solubility aluminium salt, leading to composite material, substrate material surface is by acidity during the preparation process
Solution corrodes, and surface is destroyed, and causes the compound ultimately generated specific capacity loss for the first time larger.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
Kind lithium ion battery composite cathode material and preparation method thereof, capacitance loss caused by can reduce because of cladding aluminum phosphate, guarantees
Clad uniformity improves the utilization rate of nonactive cladding substance；The crystallinity of clad is improved simultaneously, to improve cladding
The ability that layer electrolyte resistance corrodes.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A kind of lithium ion battery composite cathode material coats one on the surface of described matrix using cobalt acid lithium material as matrix
Layer mixes magnesium phosphoric acid aluminium layer.
Above-mentioned composite positive pole, it is preferred that the mass fraction that the quality for mixing magnesium phosphoric acid aluminium layer accounts for matrix is
0.05%-0.8%.
Above-mentioned composite positive pole, it is preferred that the magnesium phosphoric acid aluminium layer of mixing is that high-crystallinity mixes magnesium phosphoric acid aluminium layer.
Above-mentioned composite positive pole, it is preferred that the molecular formula of the cobalt acid lithium material is LixCo1-yMyO2；Wherein,
One or more of 0.95≤x≤1.2,0≤y≤0.1, M Mn, Cr, V, Ti, Al and Mg.
The inventive concept total as one, the present invention also provides a kind of preparation method of above-mentioned composite positive pole, packets
Include following steps:
(1) ease of solubility aluminium salt and ease of solubility magnesium salts are dissolved in solvent, obtain solution A；
(2) Diffluent phosphorus hydrochlorate is dissolved in solvent, obtains solution B；
(3) under agitation, the solution B is injected into the solution A, and controls the pH of system in reaction process
Value is 4-6, is after the reaction was completed filtered, washed resulting product, dries, and obtains unformed mixing magnesium phosphoric acid alumina particles；It reacted
Process control controls Ph, can prevent the excessively high generation Al (OH) of pH3, can also prevent pH too low and lead to (PO3)3 3-It generates or reacts
Product yield is too low；
(4) by it is described it is unformed mix magnesium phosphoric acid alumina particles and be uniformly mixed with cobalt acid lithium material, be then sintered to get arriving
The composite positive pole.
Above-mentioned preparation method, it is preferred that the ease of solubility aluminium salt is the halide of aluminum nitrate, aluminum sulfate, aluminum acetate, aluminium
One or more of；
The ease of solubility magnesium salts is selected from one or more of magnesium nitrate, magnesium sulfate, magnesium acetate, the halide of magnesium；
The Diffluent phosphorus hydrochlorate is selected from one hydrogen lithium of phosphoric acid, lithium dihydrogen phosphate, ammonium phosphate, diammonium hydrogen phosphate, biphosphate
One or more of ammonium, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate and potassium dihydrogen phosphate.
Above-mentioned preparation method, it is preferred that the solvent is the aqueous solution of water or organic matter, and the organic matter is selected from second
One or more of alcohol, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol.
Above-mentioned preparation method, it is preferred that the temperature of the sintering is 650-1000 DEG C, and the time of sintering is 4-9 hours.
Above-mentioned preparation method, it is preferred that metal cation concentration is 0.05mol/L-0.4mol/L in the solution A,
Anion concentration is 0.05mol/L-0.4mol/L in the solution B；In the solution A in metal cation and the solution B
The molar ratio range of anion is (0.8:1)-(1.1:1), Mg in the metal cation2+With Al3+Molar ratio be
(0.01-0.15):1。
Compared with the prior art, the advantages of the present invention are as follows:
(1) present invention carries out encapsulated magnesium-doped phosphoric acid aluminium layer modification to cobalt acid lithium material matrix, with AlPO4Superficial layer is compared,
The incorporation of magnesium elements improves the crystallinity of clad, improves the electrolyte resistance erosiveness of composite positive pole, Ke Yi
Longer time lower holding electrolyte is isolated with active material, and then improves cycle performance and the safety of lithium ion battery
Energy；In battery charge and discharge process, the dielectric film amount of the poorly conductive of positive electrode Surface Creation is small, battery capacity conservation rate and
Discharging, average voltage conservation rate is high, electric conductivity is strong, reduces polarization phenomena.
(2) main body decorative material is aluminum phosphate in clad of the invention, and covers most of cobalt acid lithium material matrix table
Face has played the performance of aluminum phosphate cladding so that the final floating charge performance time and high-temperature storage performance of battery are all promoted
Advantage.
(3) the unformed of nanometer particle size is first prepared during preparation method of the invention and mix magnesium aluminum phosphate, with cobalt acid lithium
After matrix mixing, can uniform adsorption is formed after substrate material surface, heat treatment and liquid phase coating uniformity coefficient is similar wraps
Coating, and avoid in liquid phase coating mode, matrix surface caused by contacting because of matrix with solvent corrodes, so as to avoid specific volume
Amount loses excessive phenomenon.
To sum up, the present invention cobalt acid lithium material matrix surface cladding it is unformed mix magnesium aluminum phosphate nanoparticles, may make and receive
Rice grain is more uniform to be adsorbed on positive electrode surface, obtains crystallinity height, continuous finishing coat through Overheating Treatment --- and it is high
The nanometer of crystallinity mixes magnesium phosphoric acid aluminium layer (specific schematic diagram is as shown in Figure 1), so that the erosion resisting of composite positive pole is more
By force, the electric discharge average voltage holding capacity and specific capacity cycle performance of battery material are improved, while remaining aluminum phosphate cladding
The high temperature resistance of layer.
Detailed description of the invention
Fig. 1 is composite positive pole heat treatment of the present invention front and back schematic diagram.
Fig. 2 is the unformed SEM picture for mixing magnesium aluminum phosphate of nanometer prepared by the embodiment of the present invention 1.
Fig. 3 is the unformed XRD diagram for mixing magnesium aluminum phosphate of nanometer prepared by the embodiment of the present invention 1.
Fig. 4 is the SEM photograph for the mixture that nanometer mixes magnesium aluminum phosphate and cobalt acid lithium matrix in the embodiment of the present invention 1.
Fig. 5 is the XRD diagram of the superficial layer for the composite positive pole that the embodiment of the present invention 1 is prepared.
Fig. 6 is that composite positive pole in the embodiment of the present invention 1, comparative example 1 and comparative example 2 is made the charge and discharge of battery and follows
Ring comparison diagram.
Fig. 7 is the electric discharge average voltage comparison that battery is made in composite positive pole in the embodiment of the present invention 2 and comparative example 4
Figure.
Specific embodiment
To facilitate the understanding of the present invention, invention herein is done below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but protection scope of the present invention is not limited to following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, and it is of the invention to be not intended to limitation
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of lithium ion battery composite cathode material of the invention, with cobalt acid lithium material, (molecular formula is
Li1.01Co0.995Mg0.002Al0.002Ti0.001O2) it is matrix, one layer is coated on the surface of matrix and mixes magnesium phosphoric acid aluminium layer, wherein is mixed
Magnesium phosphoric acid aluminium layer mixes magnesium phosphoric acid aluminium layer for high-crystallinity；Mixing magnesium phosphoric acid aluminium layer quality to account for the mass fraction of matrix is 0.5%.
The preparation method of the lithium ion battery composite cathode material of the present embodiment, comprising the following steps:
(1) 20g Al (NO is taken3)3·9H2O and 2.42g Mg (NO3)2·6H2O is dissolved in 400mL water, obtains cation
Concentration is the solution A of 0.16mol/L；
(2) 7.86g (NH is taken4)2HPO4It is dissolved in 400mL water, obtains the solution B that anion concentration is 0.15mol/L；
(3) under stirring conditions, solution B is injected into solution A, when the pH value of reaction system reaches 4, starts to drip
Add ammonium hydroxide, control the pH=5 of reaction system, all inject and finish until solution B, obtain suspension, obtained suspension is taken out
Filter, washing, drying, obtain that nanometer is unformed to mix magnesium aluminum phosphate；The SEM picture and XRD diagram that this nanometer mixes magnesium aluminum phosphate are respectively such as
Shown in Fig. 2 and Fig. 3, it is undefined structure that the nanometer, which mixes magnesium aluminum phosphate, as we know from the figure；
(4) the unformed magnesium aluminum phosphate of mixing of the nanometer for taking 5g step (3) to be prepared (is mixed with 1Kg cobalt acid lithium ball milling mixing
The SEM of object can be seen that the two is uniformly mixed as shown in Figure 4, in Fig. 4), mix products are sintered 6h at 700 DEG C, mix magnesium phosphorus
Sour aluminium is merged with matrix, is obtained to surface and is coated with the cobalt acid lithium compound for mixing magnesium aluminum phosphate, i.e. composite lithium ion battery anode material
Material, number LCO-A0.
Comparative example 1:
The difference from embodiment 1 is that uncoated processing basis material, number LCO-A1；
Comparative example 2:
The difference from embodiment 1 is that prepare it is unformed mix magnesium aluminum phosphate during, magnesium nitrate is changed into the amount of equal substances
Aluminum nitrate 3.54g, prepare unformed phosphoric acid aluminum nanopowder, and coat cobalt acid lithium matrix with the same manner, obtain compound
Material, number LCO-A2；
By unformed XRD such as Fig. 5 after mixing magnesium phosphoric acid aluminum sinter in unformed aluminum phosphate obtained in process and embodiment 1,
Know that crystallinity significantly improves after mixing magnesium, structure remains as aluminophosphate structure.
Comparative example 3:
The preparation method of the lithium ion battery composite cathode material of this comparative example, comprising the following steps:
(1) 8.3g 20g Al (NO is taken3)3·9H2O and 1.01g Mg (NO3)2·6H2O is dissolved in 200mL water, is obtained
Cation concn is the solution A of 0.16mol/L；
(2) 3.28g (NH is taken4)2HPO4It is dissolved in 200mL water, obtains the solution B that anion concentration is 0.15mol/L；
(3) under stirring conditions, solution B is injected into solution A, when the pH value of reaction system reaches 4, starts to drip
Add ammonium hydroxide, control the pH=5 of reaction system, all injects and finish until solution B, obtain suspension, 1Kg cobalt acid lithium basis material
It is added in suspension, forms slurry after mixing, dried under the conditions of adding slurry into 120 DEG C of pallet, by drying product 700
6h is sintered at DEG C, and the magnesium aluminum phosphate of mixing for coating wet process is merged with matrix, and the cobalt acid lithium for being coated with and mixing magnesium aluminum phosphate is obtained to surface
Compound, i.e. lithium ion battery composite cathode material, number LCO-A3.
The head of battery is made in lithium ion composite positive pole prepared by embodiment 1, comparative example 1, comparative example 2 and comparative example 3
Secondary specific discharge capacity is shown in Table 1, the first discharge specific capacity of the lithium ion battery of preparation method preparation of the invention only it is secondary not
It is coated processing basis material, and is higher than the first discharge specific capacity of the basis material of other methods processing；The embodiment of the present invention
1, comparative example 1, comparative example 2 cyclic specific capacity figure as shown in Figure 6；Embodiment 1 and comparative example 2 do not do matrix relative to any
For the positive electrode of the comparative example 1 of processing, charge-discharge performance increases, and composite positive pole of the invention
(mixing magnesium in phosphoric acid aluminium layer) improves the charge-discharge performance of battery more excellent for magnesium elements undoped in clad
It is different.
1 first discharge specific capacity of table
| LCO-A0 | LCO-A1 | LCO-A2 | LCO-A3 | |
| Specific discharge capacity (mAhg-1) | 212 | 214.6 | 211 | 210 |
Embodiment 2:
A kind of lithium ion battery composite cathode material of the invention is wrapped using cobalt acid lithium material as matrix on the surface of matrix
It covers one layer and mixes magnesium phosphoric acid aluminium layer, wherein mixing magnesium phosphoric acid aluminium layer is that high-crystallinity mixes magnesium phosphoric acid aluminium layer, and nanometer mixes magnesium phosphoric acid aluminium layer matter
The mass fraction that amount accounts for matrix is 0.8%；The molecular formula of cobalt acid lithium material is Li1.034Co0.995Mg0.002Al0.002Ti0.001O2。
The preparation method of the lithium ion battery composite cathode material of the present embodiment, comprising the following steps:
(1) 30g Al (NO is taken3)3·9H2O and 1.08g Mg (NO3)2·6H2O is dissolved in 200mL water, obtains cation
Concentration is the solution A of 0.42mol/L；
(2) 10.93g (NH is taken4)2HPO4It is dissolved in 200mL water, obtains the solution B that anion concentration is 0.41mol/L；
(3) under stirring conditions, solution B is injected into solution A, when the pH value of reaction system reaches 4, starts to drip
Add ammonium hydroxide, control the pH=4.5 of reaction system, all injects and finish until solution B, obtain suspension, the suspension that will be obtained
It filters, washing, drying, obtains that nanometer is unformed to mix magnesium aluminum phosphate；
(4) nanometer for taking 8g step (3) to be prepared is unformed to mix magnesium aluminum phosphate and 1Kg cobalt acid lithium ball milling mixing, will mix
It closes product and is sintered 5h at 950 DEG C, the unformed magnesium aluminum phosphate of mixing of nanometer merges with matrix, obtains to surface to be coated with and mix magnesium aluminum phosphate
Cobalt acid lithium compound, i.e. lithium ion battery composite cathode material, number LCO-B0.
Comparative example 4:
This comparative example the difference from example 2 is that: uncoated processing basis material, number LCO-B1.
Electric discharge average voltage comparison diagram such as Fig. 7 institute of composite positive pole prepared by the embodiment of the present invention 2 and comparative example 4
Show, the electric discharge average voltage that composite positive pole of the invention can significantly improve battery is horizontal.
Embodiment 3:
A kind of lithium ion battery composite cathode material of the invention, with cobalt acid lithium material, (molecular formula is
Li0.99Co0.995Mg0.002Al0.002Ti0.001O2) it is matrix, one layer is coated on the surface of matrix and mixes magnesium phosphoric acid aluminium layer, wherein is received
It is that high-crystallinity mixes magnesium aluminum phosphate that rice, which mixes magnesium phosphoric acid aluminium layer, and it is 1% that nanometer, which mixes magnesium aluminum phosphate covering amount,.
The preparation method of the lithium ion battery composite cathode material of the present embodiment, comprising the following steps:
(1) 30g Al is taken2(SO4)3With 2.11g MgSO4It is dissolved in 1L water, obtaining cation concn is 0.1mol/L's
Solution A；
(2) 13g (NH is taken4)2HPO4It is dissolved in 1L water, obtaining anion concentration is 0.1mol/L solution B；
(3) under stirring conditions, solution B is injected into solution A, when the pH value of reaction system reaches 4, starts to drip
Add ammonium hydroxide, control the pH=5.5 of reaction system, all injects and finish until solution B, obtain suspension, the suspension that will be obtained
It filters, washing, drying, obtains that nanometer is unformed to mix magnesium aluminum phosphate；
(4) nanometer for taking 10g step (3) to be prepared is unformed to mix magnesium aluminum phosphate and 1Kg cobalt acid lithium ball milling mixing, will mix
It closes product and is sintered 8h at 650 DEG C, the unformed magnesium aluminum phosphate of mixing of nanometer merges with matrix, obtains to surface to be coated with and mix magnesium aluminum phosphate
Cobalt acid lithium compound, i.e. lithium ion battery composite cathode material, number LCO-C0.
Comparative example 5:
The difference of this comparative example and embodiment 3 is: uncoated processing basis material, number LCO-C1.
Comparative example 6:
The difference of this comparative example and embodiment 3 is: aluminum sulfate being changed to magnesium sulfate, unformed magnesium nitrate is prepared, with same
Sample loading mode carries out cladding processing to matrix, obtains composite material, number LCO-C2.
Battery is made in the composite positive pole of embodiment 3, comparative example 5, comparative example 6, under the conditions of 60 DEG C, battery is filled
Electricity is to 4.55V, and constant-voltage charge, time of the record constant-voltage charge to electric current greater than 0.05mA, tests its floating charge performance, as a result such as
Shown in table 2.
2 floating charge performance test of table experiment
| LCO-C0 | LCO-C1 | LCO-C2 | |
| Floating charge performance time (h) | 132.5 | 90 | 102 |
Embodiment 4:
A kind of lithium ion battery composite cathode material of the invention, with cobalt acid lithium material, (molecular formula is
Li0.99Co0.994Mg0.002Al0.003Ti0.001O2) it is matrix, one layer is coated on the surface of matrix and mixes magnesium phosphoric acid aluminium layer, wherein is mixed
Magnesium phosphoric acid aluminium layer is that highly crystalline state mixes magnesium aluminum phosphate, and it is 0.8% that nanometer, which mixes magnesium aluminum phosphate covering amount,.
The preparation method of the lithium ion battery composite cathode material of the present embodiment, comprising the following steps:
(1) 20.9g Al (NO is taken3)3·9H2O and 0.75g Mg (NO3)2·6H2O is dissolved in the mixed of 200mL alcohol and water
(volume ratio of water and alcohol is 2:1) is closed in solution, the solution A that cation concn is 0.29mol/L is obtained；
(2) 7.69g (NH is taken4)2HPO4It is dissolved in the mixed solution of 200mL alcohol and water that (volume ratio of water and alcohol is
2:1), the solution B that anion concentration is 0.29mol/L is obtained；
(3) under stirring conditions, solution B is injected into solution A, when the pH value of reaction system reaches 4, starts to drip
Add ammonium hydroxide, control the pH=4.5 of reaction system, all injects and finish until solution B, obtain suspension, the suspension that will be obtained
It filters, washing, drying, obtains that nanometer is unformed to mix magnesium aluminum phosphate；
(4) nanometer for taking 8g step (3) to be prepared is unformed to mix magnesium aluminum phosphate and 1Kg cobalt acid lithium ball milling mixing, will mix
It closes product progress and is sintered 6h at 800 DEG C, the unformed magnesium aluminum phosphate of mixing of nanometer merges with matrix, obtains to surface to be coated with and mix magnesium phosphorus
The cobalt acid lithium compound of sour aluminium, i.e. lithium ion battery composite cathode material, number LCO-D0.
Comparative example 7:
The difference of this comparative example and embodiment 7 is: uncoated processing basis material, number LCO-D1.
Rectangular cell storage volume swell increment at high temperature is made in the composite positive pole of testing example 4 and comparative example 7,
It is shown in Table 3, after carrying out high temperature storage under the conditions of 85 DEG C/6h and 90 DEG C/6h, embodiment 4 is because of thickness caused by battery flatulence
Incrementss are significantly less than comparative example, and the high-temperature storage performance of embodiment is more excellent.
3 rectangular cell high temperature storage volume expansion amount of table
| 85℃/6h | 90℃/6h | |
| LCO-D1 | 17.7% | 45.2% |
| LCO-D0 | 9.8% | 26.0% |
Experiment condition: positive electrode is prepared into rectangular cell, tests cell thickness, then battery is put under hot conditions and is deposited
Certain time, re-test cell thickness are stored up, and calculates the increased percentage of cell thickness.
Claims (9)
1. a kind of lithium ion battery composite cathode material, which is characterized in that the composite positive pole is using cobalt acid lithium material as base
Body coats one layer on the surface of described matrix and mixes magnesium phosphoric acid aluminium layer.
2. composite positive pole as described in claim 1, which is characterized in that the quality for mixing magnesium phosphoric acid aluminium layer accounts for matrix
Mass fraction is 0.05%-0.8%.
3. composite positive pole as described in claim 1, which is characterized in that the magnesium phosphoric acid aluminium layer of mixing is mixing for high-crystallinity
Magnesium phosphoric acid aluminium layer.
4. composite positive pole as described in any one of claims 1-3, which is characterized in that the molecular formula of the cobalt acid lithium material
For LixCo1-yMyO2；Wherein, one or more of 0.95≤x≤1.2,0≤y≤0.1, M Mn, Cr, V, Ti, Al and Mg.
5. a kind of preparation method such as composite positive pole of any of claims 1-4, which is characterized in that including with
Lower step:
(1) ease of solubility aluminium salt and ease of solubility magnesium salts are dissolved in solvent, obtain solution A；
(2) Diffluent phosphorus hydrochlorate is dissolved in solvent, obtains solution B；
(3) under agitation, the solution B is injected into the solution A, and the pH value for controlling system in reaction process is
Resulting product is filtered, washed after the reaction was completed, dries by 4-6, obtains unformed mixing magnesium phosphoric acid alumina particles；
(4) by it is described it is unformed mix magnesium phosphoric acid alumina particles and be uniformly mixed with cobalt acid lithium material, be then sintered to get to described
Composite positive pole.
6. preparation method as claimed in claim 5, which is characterized in that the ease of solubility aluminium salt is aluminum nitrate, aluminum sulfate, aluminium
One or more of halide；
The ease of solubility magnesium salts is selected from one or more of magnesium nitrate, magnesium sulfate, magnesium acetate, the halide of magnesium；
The Diffluent phosphorus hydrochlorate is selected from one hydrogen lithium of phosphoric acid, lithium dihydrogen phosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, phosphorus
One or more of sour sodium, disodium hydrogen phosphate, sodium dihydrogen phosphate, potassium phosphate, dipotassium hydrogen phosphate and potassium dihydrogen phosphate.
7. preparation method as claimed in claim 5, which is characterized in that the solvent is the aqueous solution of water or organic matter, described
Organic matter is selected from one or more of ethyl alcohol, polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol.
8. preparation method as claimed in claim 5, which is characterized in that the temperature of the sintering is 650-1000 DEG C, sintering
Time is 4-9 hours.
9. preparation method as claimed in claim 5, which is characterized in that metal cation concentration is in the solution A
0.05mol/L-0.4mol/L, anion concentration is 0.05mol/L-0.4mol/L, metal in the solution A in the solution B
The cationic molar ratio range with anion in the solution B is (0.8:1)-(1.1:1), Mg in the metal cation2+
With Al3+Molar ratio be (0.01-0.15): 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711122689.5A CN109786679B (en) | 2017-11-14 | 2017-11-14 | Composite positive electrode material of lithium ion battery and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711122689.5A CN109786679B (en) | 2017-11-14 | 2017-11-14 | Composite positive electrode material of lithium ion battery and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109786679A true CN109786679A (en) | 2019-05-21 |
| CN109786679B CN109786679B (en) | 2021-05-11 |
Family
ID=66493493
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711122689.5A Active CN109786679B (en) | 2017-11-14 | 2017-11-14 | Composite positive electrode material of lithium ion battery and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109786679B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111092213A (en) * | 2019-12-31 | 2020-05-01 | 河南电池研究院有限公司 | Composite positive electrode material of lithium ion battery and preparation method thereof |
| CN111106344A (en) * | 2019-12-31 | 2020-05-05 | 天目湖先进储能技术研究院有限公司 | Composite positive electrode material, preparation method and lithium battery |
| CN111584153A (en) * | 2020-05-27 | 2020-08-25 | 江苏纳欧新材料有限公司 | Method for preparing white rod-shaped conductive material by using attapulgite as template |
| CN112938918A (en) * | 2019-12-10 | 2021-06-11 | 湖南杉杉能源科技股份有限公司 | Preparation method of cobalt phosphate powder material |
| CN114447323A (en) * | 2022-02-14 | 2022-05-06 | 山东威固新能源科技有限公司 | Lithium metal material with phosphate coating on surface and preparation method and application thereof |
| CN117254020A (en) * | 2023-11-13 | 2023-12-19 | 江门市科恒实业股份有限公司 | Aluminum phosphate coated calcium-doped sodium ion battery positive electrode material and preparation method thereof |
| CN114447323B (en) * | 2022-02-14 | 2024-06-04 | 山东威固新能源科技有限公司 | Lithium metal material with surface having phosphate layer, and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040258836A1 (en) * | 2003-06-23 | 2004-12-23 | Besenhard Jurgen Otto | Method for the synthesis of surface-modified materials |
| CN102842705A (en) * | 2011-06-22 | 2012-12-26 | 清华大学 | Cobalt oxide and composite material thereof, and preparation method of cobalt oxide composite material |
| CN103199258A (en) * | 2013-03-07 | 2013-07-10 | 中航锂电（洛阳）有限公司 | Cathode material of lithium ion battery, preparation method of cathode, and lithium ion battery |
| CN105070899A (en) * | 2015-08-07 | 2015-11-18 | 田东 | Preparation method of lithium-ion power battery anode material |
| CN106505194A (en) * | 2016-12-19 | 2017-03-15 | 惠州Tcl金能电池有限公司 | Modified cobalt acid lithium and preparation method thereof, lithium ion battery and its chemical synthesizing method |
-
2017
- 2017-11-14 CN CN201711122689.5A patent/CN109786679B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040258836A1 (en) * | 2003-06-23 | 2004-12-23 | Besenhard Jurgen Otto | Method for the synthesis of surface-modified materials |
| CN102842705A (en) * | 2011-06-22 | 2012-12-26 | 清华大学 | Cobalt oxide and composite material thereof, and preparation method of cobalt oxide composite material |
| CN103199258A (en) * | 2013-03-07 | 2013-07-10 | 中航锂电（洛阳）有限公司 | Cathode material of lithium ion battery, preparation method of cathode, and lithium ion battery |
| CN105070899A (en) * | 2015-08-07 | 2015-11-18 | 田东 | Preparation method of lithium-ion power battery anode material |
| CN106505194A (en) * | 2016-12-19 | 2017-03-15 | 惠州Tcl金能电池有限公司 | Modified cobalt acid lithium and preparation method thereof, lithium ion battery and its chemical synthesizing method |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112938918A (en) * | 2019-12-10 | 2021-06-11 | 湖南杉杉能源科技股份有限公司 | Preparation method of cobalt phosphate powder material |
| CN111092213A (en) * | 2019-12-31 | 2020-05-01 | 河南电池研究院有限公司 | Composite positive electrode material of lithium ion battery and preparation method thereof |
| CN111106344A (en) * | 2019-12-31 | 2020-05-05 | 天目湖先进储能技术研究院有限公司 | Composite positive electrode material, preparation method and lithium battery |
| CN111106344B (en) * | 2019-12-31 | 2022-05-06 | 天目湖先进储能技术研究院有限公司 | Composite positive electrode material, preparation method and lithium battery |
| CN111092213B (en) * | 2019-12-31 | 2023-01-31 | 河南电池研究院有限公司 | Composite positive electrode material of lithium ion battery and preparation method thereof |
| CN111584153A (en) * | 2020-05-27 | 2020-08-25 | 江苏纳欧新材料有限公司 | Method for preparing white rod-shaped conductive material by using attapulgite as template |
| CN114447323A (en) * | 2022-02-14 | 2022-05-06 | 山东威固新能源科技有限公司 | Lithium metal material with phosphate coating on surface and preparation method and application thereof |
| CN114447323B (en) * | 2022-02-14 | 2024-06-04 | 山东威固新能源科技有限公司 | Lithium metal material with surface having phosphate layer, and preparation method and application thereof |
| CN117254020A (en) * | 2023-11-13 | 2023-12-19 | 江门市科恒实业股份有限公司 | Aluminum phosphate coated calcium-doped sodium ion battery positive electrode material and preparation method thereof |
| CN117254020B (en) * | 2023-11-13 | 2024-03-08 | 江门市科恒实业股份有限公司 | Aluminum phosphate coated calcium-doped sodium ion battery positive electrode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109786679B (en) | 2021-05-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109786679A (en) | A kind of lithium ion battery composite cathode material and preparation method thereof | |
| CN110858643B (en) | Fast ion conductor modified lithium ion battery cathode material and preparation method thereof | |
| CN104025347B (en) | Manufacturing method, the manufacturing method of electrode plate of electrode material, electrode plate, lithium ion battery and electrode material | |
| CN107069006A (en) | A kind of method for improving the nickelic tertiary cathode material chemical property of lithium ion battery | |
| CN106684369A (en) | Sodium super ionic conductor-inlaid and coated positive electrode material for sodium-ion battery and synthesis method of positive electrode material | |
| CN108550833A (en) | A kind of positive electrode and lithium ion battery | |
| CN106910874B (en) | A kind of surface cladding Li2TiO3With the high-nickel material and preparation method of surface layer doping Ti | |
| CN106058225A (en) | LiMn1-XFexPO4 positive electrode material having core-shell structure, and preparation method thereof, and lithium ion battery | |
| CN108550814B (en) | Preparation method and application of modified sodium vanadium fluorophosphate cathode material | |
| CN102347471A (en) | Lithium-nickel-cobalt-manganese oxide composite material particle and preparation method thereof as well as battery | |
| CN106257718B (en) | A kind of BN cladding is without cobalt Ni-Mn solid solution nickel hydroxide base anode materials | |
| CN106410157A (en) | High-magnification long-service-life anode material and preparation method thereof | |
| CN107681152A (en) | Secondary lithium batteries lithium composite xoide and preparation method thereof | |
| CN106898775A (en) | Double cladded type richness lithium materials in a kind of surface and preparation method thereof | |
| CN107681150A (en) | Secondary lithium batteries lithium composite xoide and preparation method thereof | |
| CN107768642A (en) | A kind of lithium ion battery ternary material of surface double cladding and preparation method thereof | |
| CN107611355A (en) | Secondary lithium batteries lithium composite xoide and preparation method thereof | |
| CN105428621B (en) | A kind of lithium ion conductor cladding nanometer LiMnPO4The method of modifying of/C positive electrode material | |
| EP3561919A1 (en) | Cathode active material, method for preparing same, and lithium secondary battery comprising same | |
| WO2022205667A1 (en) | Silicon-based negative electrode material, and preparation method therefor and application thereof | |
| CN113851624A (en) | Composite cathode material and preparation method and application thereof | |
| CN102447105A (en) | Lithium nickel oxide composite material and preparation method thereof and lithium ion battery | |
| CN105185992A (en) | Carbon-lithium iron phosphate multi-phase and single-layer co-coated lithium ferric manganese phosphate material and preparation method thereof | |
| CN110148712A (en) | A kind of rich lithium manganese anode material and preparation method thereof that compound coating is modified | |
| CN105244481B (en) | A kind of carbon-coated LiFePO 4 for lithium ion batteries positive electrode in situ and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 17-8, Lutian Road, high tech Development Zone, Changsha City, Hunan Province, 410205 Patentee after: BASF Shanshan battery material Co.,Ltd. Address before: 17-8, Lutian Road, high tech Development Zone, Changsha City, Hunan Province, 410205 Patentee before: Hunan Shanshan Energy Technology Co.,Ltd. Address after: 17-8, Lutian Road, high tech Development Zone, Changsha City, Hunan Province, 410205 Patentee after: Hunan Shanshan Energy Technology Co.,Ltd. Address before: 17-8, Lutian Road, high tech Development Zone, Changsha City, Hunan Province, 410205 Patentee before: HUNAN SHANSHAN ENERGY TECHNOLOGY Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |