CN109860570A - A kind of cobalt acid lithium-iron phosphate compound anode material of lithium and preparation method thereof - Google Patents
A kind of cobalt acid lithium-iron phosphate compound anode material of lithium and preparation method thereof Download PDFInfo
- Publication number
- CN109860570A CN109860570A CN201910149583.7A CN201910149583A CN109860570A CN 109860570 A CN109860570 A CN 109860570A CN 201910149583 A CN201910149583 A CN 201910149583A CN 109860570 A CN109860570 A CN 109860570A
- Authority
- CN
- China
- Prior art keywords
- lithium
- cobalt
- preparation
- positive electrode
- shell
- 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.)
- Withdrawn
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
Abstract
The present invention provides a kind of cobalt acid lithium-iron phosphate compound anode material of lithium and preparation method thereof.Composite positive pole provided by the invention mainly includes two kinds of ingredients of cobalt acid lithium and LiFePO4, and presentation cobalt acid lithium is core, the core-shell structure that LiFePO4 is shell, its preparation step mainly includes the preparation of cobalt acid lithium core, the preparation of LiFePO4 shell and conductive cladding processing, finally obtains composite cathode active material.Positive electrode of the invention has core-shell structure, its stratum nucleare plays high capacity, high voltage characteristics, shell plays high security characteristic, while the material shows superior electronics and ionic conductivity, has a good application prospect in high power, high-energy density and high-safety lithium battery.Of the invention preparation is simple, is easy to be mass produced, and low in cost, environmental-friendly.
Description
Technical field
The invention belongs to lithium battery manufacturing fields, and in particular to a kind of cobalt acid lithium-iron phosphate compound anode material of lithium and its
Preparation method.
Background technique
The features such as lithium ion battery with its memory-less effect, the service life is long, and pollution is few, in our life extensively
Ground application is deep into mobile electronic device and hybrid vehicle every field.
LiFePO 4 material is the power lithium-ion battery anode material for occurring and obtaining extensive industrial application in recent years
Material.This positive electrode has the special advantages such as safety is good, resourceful, discharge platform is stable and has extended cycle life.But
The discharge capacity of traditional LiFePO 4 material is lower, and discharge voltage plateau is lower, is not able to satisfy current new energy neck increasingly
Demand of the domain to high-energy density and high capacity density lithium battery.Meanwhile the electron conduction of LiFePO 4 material is poor, it is necessary to
Carry out the big battery charge-discharge power demand that conducting function processing is just able to satisfy battery.Meanwhile cobalt acid lithium is that 3C class lithium battery makes extensively
The theoretical capacity of positive electrode active materials, the material is up to 274mAh/g.But material cobalt acid lithium in charge and discharge process
Intercalation/abjection lithium ion after, crystalline structure can become unstable, Yi Fasheng irreversible transition, to make circulating battery
Service life greatly reduce, and at material and electrolyte interface Co dissolution can occur under high voltages, that electrolyte is oxidized etc. is secondary anti-
It answers, further decreases material lifetime.
Therefore, become current hot spot for the study on the modification of above two material.For LiFePO 4 material.Mainly grind
Study carefully influence of the method for modifying such as ion doping, carbon coating and material nano to lithium-ion battery lithium iron phosphate positive electrode；
For cobalt acid lithium material, mainly from improve structural stability and reduce interface side reaction two in terms of be designed, such as by magnesium,
The lifetime stability of cobalt acid lithium can be improved in the doping of the elements such as aluminium, zirconium, titanium.But doped chemical and cladding often cause compared with
More capacitance loss.
Summary of the invention
In view of above-mentioned analysis, for overcome the deficiencies in the prior art, the present invention is from the angle of Material cladding, by above-mentioned two class
Battery active material carries out high efficiency composition, so that material property can be realized mutual supplement with each other's advantages, maximized favourable factors and minimized unfavourable ones, effectively improves lithium battery
Comprehensive performance promotes lithium battery in the expansion of the application fields such as high-energy density, high capacity density and high security.
A kind of cobalt acid lithium-iron phosphate compound anode material of lithium provided by the invention and preparation method thereof, the anode composite material
Expect that there is the core-shell structure that cobalt acid lithium is core, LiFePO4 is shell, there is high capacity, height with composite positive pole prepared by this side
The characteristics such as voltage and high security, while showing good service life, have in new energy field lithium battery good
Application prospect.Of the invention preparation is simple, is easy to be mass produced, and low in cost, environmental-friendly.
It is an object of the present invention to provide a kind of positive electrode for battery material, the positive electrode includes core-shell structure,
Stratum nucleare in the core-shell structure includes cobalt acid lithium, and shell includes LiFePO4.
At least one of specifically, the positive electrode further includes following 1) -8) described:
1) diameter of stratum nucleare includes 0.5~10 μm；
2) thickness of shell includes 0.2~5 μm；
It combines closely between core, shell, without obvious layering；
3) average grain diameter of the positive electrode includes 0.7~15 μm；
4) specific surface area of the positive electrode includes 0.25~0.85m2/g；
5) discharge voltage plateau of the positive electrode is 3.2~4.2V；
6) the 0.5C current density discharge capacity of the positive electrode includes 160~270mAh/g；
7) preparation method of the stratum nucleare includes: that cobalt salt and alkaline solution are prepared into ball shaped hydroxy using hydro-thermal reaction method
Cobalt oxide；Gained spherical hydroxy cobalt oxide is placed in lithium hydroxide aqueous solution, the hydrogen in lithium ion displacement hydroxy cobalt oxide is made
Up to cobalt acid lithium；
8) preparation method of the shell includes: that the compound respectively containing lithium, iron and/or phosphorus is dissolved in containing cobalt acid lithium
In the deionized water of powder, the compound containing lithium, iron and/or phosphorus generates LiFePO4 respectively, and complexing agent, heating stirring is added
And ultrasonication, jel product is obtained, dry, ball mill grinding obtains powder, in an inert atmosphere roasting and/or agglomerated powder
Body is up to electrode material granules.
At least one of again specifically, the positive electrode further includes following 1) -10) described:
1) preparation method of the stratum nucleare further include: by the cobalt acid lithium being prepared filtering, drying；
2) cobalt salt includes cobalt chloride, cobalt acetate and/or cobalt nitrate；
3) alkaline solution includes sodium hydroxide solution, potassium hydroxide solution and/or sodium carbonate liquor；
4) mass ratio of the hydroxy cobalt oxide and lithium hydroxide includes 5~10:1；
5) complexing agent includes monoethanolamine, diethanol amine, tartaric acid and/or citric acid；
6) in the preparation method of the shell, cobalt acid lithium: LiFePO4: the molar ratio of complexing agent includes 1:0.05~0.5:
0.01~0.2；
7) temperature of the roasting and/or sintering includes 550 DEG C~1400 DEG C；
8) inert atmosphere includes nitrogen atmosphere；
9) molar ratio and LiFePO of the compound respectively containing lithium, iron and/or phosphorus4In lithium, iron and phosphate radical
Molar ratio it is consistent；
10) preparation method of the shell further includes conductive cladding processing: dispersing chloroform for poly-triphenylamine powder
In conducting function treatment fluid, then the electrode material granules are dispersed in the conducting function treatment fluid, stirring, mistake
Filter, dry, ball mill grinding are to get positive electrode；Specifically, the mass concentration of the conducting function treatment fluid includes 1.5%
~4.5%；And/or specifically, the mass ratio of the electrode material granules and poly-triphenylamine includes 20~50:1.
It is also another object of the present invention to provide a kind of preparation method of positive electrode for battery material, the positive electrode includes
Core-shell structure, the stratum nucleare in the core-shell structure includes cobalt acid lithium, and shell includes LiFePO4, the preparation side of the positive electrode
Method include it is following 1) and/or 2):
1) preparation method of the stratum nucleare includes: that cobalt salt and alkaline solution are prepared into ball shaped hydroxy using hydro-thermal reaction method
Cobalt oxide；Gained spherical hydroxy cobalt oxide is placed in lithium hydroxide aqueous solution, the hydrogen in lithium ion displacement hydroxy cobalt oxide is made
Up to cobalt acid lithium；
2) preparation method of the shell includes: that the compound respectively containing lithium, iron and/or phosphorus is dissolved in containing cobalt acid lithium
Deionized water in, compound containing lithium, iron and/or phosphorus generates LiFePO4 respectively, and complexing agent is added, and heating stirring simultaneously surpasses
Sonicated obtains jel product, and dry, ball mill grinding obtains powder, roasts and/or is sintered powder in an inert atmosphere and be
Obtain electrode material granules.
At least one of specifically, the method also includes following 1) -16) described:
1) preparation method of the stratum nucleare further include: by the cobalt acid lithium being prepared filtering, drying；
2) cobalt salt includes cobalt chloride, cobalt acetate and/or cobalt nitrate；
3) alkaline solution includes sodium hydroxide solution, potassium hydroxide solution and/or sodium carbonate liquor；
4) mass ratio of the hydroxy cobalt oxide and lithium hydroxide includes 5~10:1；
5) complexing agent includes monoethanolamine, diethanol amine, tartaric acid and/or citric acid；
6) in the preparation method of the shell, cobalt acid lithium: LiFePO4: the molar ratio of complexing agent includes 1:0.05~0.5:
0.01~0.2；
7) temperature of the roasting and/or sintering includes 550 DEG C~1400 DEG C；
8) inert atmosphere includes nitrogen atmosphere；
9) molar ratio and LiFePO of the compound respectively containing lithium, iron and/or phosphorus4In lithium, iron and phosphate radical
Molar ratio it is consistent；
10) preparation method of the shell further includes conductive cladding processing: dispersing chloroform for poly-triphenylamine powder
In conducting function treatment fluid, then the electrode material granules are dispersed in the conducting function treatment fluid, stirring, mistake
Filter, dry, ball mill grinding are to get positive electrode；
Specifically, the mass concentration of the conducting function treatment fluid includes 1.5%~4.5%；And/or specifically, institute
The mass ratio for stating electrode material granules and poly-triphenylamine includes 20~50:1；
11) diameter of stratum nucleare includes 0.5~10 μm；
12) thickness of shell includes 0.2~5 μm；
It combines closely between core, shell, without obvious layering；
13) average grain diameter of the positive electrode includes 0.7~15 μm；
14) specific surface area of the positive electrode includes 0.25~0.85m2/g；
15) discharge voltage plateau of the positive electrode is 3.2~4.2V；
16) the 0.5C current density discharge capacity of the positive electrode includes 160~270mAh/g.
It is also another object of the present invention to provide the positive electrodes that any the method for the present invention is directly prepared.
It is also another object of the present invention to provide any positive electrode of the present invention and/or any the methods of the present invention
Application.
Specifically, the application includes being used to prepare lithium battery and/or its Related product.
Of the invention a further object is provides a kind of lithium battery, and the lithium battery includes following 1) -2) it is described in extremely
Few one kind:
1) any positive electrode of the present invention；
2) preparation method includes: that any positive electrode of the present invention is assembled into lithium battery.
Of the invention a further object is provides a kind of preparation method of lithium battery, and the method includes the present invention is any
The positive electrode is assembled into lithium battery.
Unless otherwise specified, percentage according to the present invention is mass percent.
The advantages of the present invention are:
Cobalt acid lithium-iron phosphate compound anode material of lithium provided by the invention is specially by core, LiFePO4 of cobalt acid lithium
The core-shell structure of shell, stratum nucleare play high capacity, high voltage characteristics, and shell plays high security characteristic, while the material is shown
Superior electronics and ionic conductivity out have good application in high power, high-energy density and high-safety lithium battery
Prospect.The high voltage, high capacity are between voltage platform, the theoretical discharge capacity of two kinds of materials of cobalt acid lithium and LiFePO4
Between, specific value is according to core, the rate fluctuations of shell material, voltage platform 3.2-4.2V, discharge capacity 160-270mAh/
g.The high security is provided by LiFePO4, avoids charge and discharge process to the lattice damage of cobalt acid lithium material.
The lithium battery that method produced according to the present invention obtains cobalt acid lithium-iron phosphate compound anode material of lithium, effectively gram
The shortcomings that having taken unitary electrode active material, reconciled two kinds of materials the advantages of, show good charge/discharge capacity and charge and discharge
Piezoelectric voltage platform, and there is longer service life cycle, superior application prospect is shown in high performance lithium ion battery.This
The preparation method of the invention combination electrode material, has simple process, and process cycle is short, energy conservation and environmental protection, is suitble to scale
The characteristics of production.
Specific embodiment
Processing as used in the following examples or experimental method are conventional method unless otherwise specified.
Material as used in the following examples etc., is commercially available unless otherwise specified.
Following embodiments and its illustrate for explanation and understanding the present invention, do not constitute to improper limit of the invention
It is fixed.
In following embodiments unless otherwise specified, the percentage being related to is mass percent.
Embodiment 1
(1) cobalt acid lithium-iron phosphate compound anode material of lithium preparation
The preparation of cobalt acid lithium core: it takes 5.5g cobalt chloride that the sodium hydroxide solution that 60ml concentration is 12% is added, is placed in reaction
In kettle, further the hydrothermal synthesis 8h at 130 DEG C obtains the hydroxyl oxygen that partial size is about 6.5 μm after filter paper filtering, 80 DEG C of dryings
Change cobalt granule.It takes appropriate hydroxy cobalt oxide to add to the lithium hydroxide that concentration is 10%, keeps hydroxy cobalt oxide and lithium hydroxide
Mass ratio is 5:1, and 3.5h is heat-treated at 80 DEG C, obtains suspension.Using filter paper filtering, 120 DEG C of dryings, cobalt acid lithium grain is obtained
Son.
The preparation of LiFePO4 shell: according to LiFePO4In molar ratio take lithium carbonate, ferric sulfate and ammonium hydrogen phosphate to be dissolved in
In deionized water, above-mentioned cobalt acid lithium particle and tartaric acid is then added, final cobalt acid lithium: LiFePO4: the molar ratio of tartaric acid
For 1:0.1:0.03, mechanical stirring 6h obtains uniform mixture under 200 turns/min.Mixture 7h, filter paper are handled at 60 DEG C
100 DEG C of vacuum drying, obtain jel product after filtering, and ball mill grinding for 24 hours, obtains powder in nitrogen under further 600 turns/min
In 650 DEG C of sintering 20h are raised to the rate of 6 DEG C/min, cooled to room temperature obtains combination electrode material.
Conductive cladding processing: the chloroform soln 100ml for the poly-triphenylamine that compound concentration is 1.8% is added appropriate multiple
Composite electrode material is allowed to be then 30:1 is filtered at 40 DEG C, stir process 2h under 150 turns/min with the mass ratio of poly-triphenylamine
Paper misgivings, 100 DEG C of dryings, further across 1200 turns/min ball-milling treatment for 24 hours, obtain combination electrode material of the present invention.
(2) electrode material performance test:
Scanning electron microscope test result: about 7 μm of the stratum nucleare diameter of composite material, about 1.5 μm of shell thickness, whole partial size is about
10 μm, specific surface area 0.5m2/g；
Battery performance test: the material is tested with lithium piece composition half-cell, discharge voltage plateau 3.75V, 0.5C
Current density discharge capacity reaches 190mAh/g, capacity retention ratio about 85% after cycle charge-discharge 300 times under 1C electric current.
Embodiment 2
(1) cobalt acid lithium-iron phosphate compound anode material of lithium preparation
The preparation of cobalt acid lithium core: it takes 10g cobalt nitrate that the sodium carbonate liquor that 100ml concentration is 15% is added, is placed in reaction kettle
In, further the hydrothermal synthesis 6h at 150 DEG C, after filter paper filtering, 50 DEG C of dryings, obtains the hydroxyl oxidation that partial size is about 3.2 μm
Cobalt granule.It takes appropriate hydroxy cobalt oxide to add to the lithium hydroxide that concentration is 10%, keeps the matter of hydroxy cobalt oxide and lithium hydroxide
Amount is heat-treated 3h at 80 DEG C, obtains suspension than being 8:1.Using filter paper filtering, 120 DEG C of dryings, cobalt acid lithium particle is obtained.
The preparation of LiFePO4 shell: according to LiFePO4Middle molar ratio takes lithium chloride, iron chloride and ammonium hydrogen phosphate to be dissolved in
In ionized water, above-mentioned cobalt acid lithium particle and diethanol amine is then added, final cobalt acid lithium: LiFePO4: mole of ethylene glycol amine
Than for 1:0.35:0.1, mechanical stirring 8h obtains uniform mixture under 100 turns/min.Mixture 4h is handled at 60 DEG C, is filtered
100 DEG C of vacuum drying after paper filtering, obtain jel product, and ball mill grinding 48h under further 400 turns/min obtains powder in nitrogen
800 DEG C of sintering 16h are raised to the rate of 6 DEG C/min in gas, cooled to room temperature obtains combination electrode material.
Conductive cladding processing: the chloroform soln 100ml for the poly-triphenylamine that compound concentration is 3.8% is added appropriate multiple
Composite electrode material is allowed to be then 20:1 is filtered at 40 DEG C, stir process 2h under 100 turns/min with the mass ratio of poly-triphenylamine
Paper misgivings, 100 DEG C of dryings, further across 1000 turns/min ball-milling treatment for 24 hours, obtain combination electrode material of the present invention.
(2) electrode material performance test:
Scanning electron microscope test result: about 3.5 μm of the stratum nucleare diameter of composite material, about 0.6 μm of shell thickness, whole partial size
About 4.7 μm, specific surface area 0.8m2/g；
Battery performance test: the material is tested with lithium piece composition half-cell, discharge voltage plateau 3.9V, 0.5C electricity
Current density discharge capacity reaches 215mAh/g, capacity retention ratio about 91% after cycle charge-discharge 300 times under 1C electric current.
Embodiment 3
(1) cobalt acid lithium-iron phosphate compound anode material of lithium preparation
The preparation of cobalt acid lithium core: it takes 8.5g cobalt acetate that the potassium hydroxide solution that 200ml concentration is 12% is added, is placed in reaction
In kettle, further the hydrothermal synthesis 4h at 180 DEG C obtains the hydroxyl oxygen that partial size is about 9.5 μm after filter paper filtering, 50 DEG C of dryings
Change cobalt granule.It takes appropriate hydroxy cobalt oxide to add to the lithium hydroxide that concentration is 15%, keeps hydroxy cobalt oxide and lithium hydroxide
Mass ratio is 10:1, and 3h is heat-treated at 80 DEG C, obtains suspension.Using filter paper filtering, 120 DEG C of dryings, cobalt acid lithium grain is obtained
Son.
The preparation of LiFePO4 shell: according to LiFePO4Middle molar ratio takes lithium carbonate, ferric nitrate and ammonium hydrogen phosphate to be dissolved in
In ionized water, above-mentioned cobalt acid lithium particle and citric acid is then added, final cobalt acid lithium: LiFePO4: the molar ratio of citric acid is
Mechanical stirring 8h obtains uniform mixture under 1:0.5:0.02,100 turns/min.Mixture 4h, filter paper mistake are handled at 60 DEG C
100 DEG C of vacuum drying after filter, obtain jel product, and ball mill grinding 15h under further 600 turns/min obtains powder in nitrogen
1200 DEG C of sintering 3h are raised to the rate of 6 DEG C/min, cooled to room temperature obtains combination electrode material.
Conductive cladding processing: the chloroform soln 100ml for the poly-triphenylamine that compound concentration is 2% is added appropriate compound
Electrode material is allowed to the mass ratio of poly-triphenylamine be 25:1, at 40 DEG C, stir process 2h under 100 turns/min, then filter paper
Misgivings, 100 DEG C of dryings obtain combination electrode material of the present invention further across the ball-milling treatment 16h of 1200 turns/min.
(2) electrode material performance test:
Scanning electron microscope test result: about 10 μm of the stratum nucleare diameter of composite material, about 2.5 μm of shell thickness, whole partial size
About 15 μm, specific surface area 0.25m2/g；
Battery performance test: the material is tested with lithium piece composition half-cell, discharge voltage plateau 3.75V, 0.5C
Current density discharge capacity reaches 205mAh/g, capacity retention ratio about 88% after cycle charge-discharge 300 times under 1C electric current.
Embodiment 4
(1) cobalt acid lithium-iron phosphate compound anode material of lithium preparation
The preparation of cobalt acid lithium core: it takes 12g cobalt chloride that the sodium carbonate liquor that 100ml concentration is 15% is added, is placed in reaction kettle
In, further the hydrothermal synthesis 2h at 120 DEG C, after filter paper filtering, 50 DEG C of dryings, obtains the hydroxyl oxidation that partial size is about 0.5 μm
Cobalt granule.It takes appropriate hydroxy cobalt oxide to add to the lithium hydroxide that concentration is 5%, keeps the quality of hydroxy cobalt oxide and lithium hydroxide
Than for 6:1, being heat-treated 1h at 60 DEG C, suspension is obtained.Using filter paper filtering, 100 DEG C of dryings, cobalt acid lithium particle is obtained.
The preparation of LiFePO4 shell: according to LiFePO4Middle molar ratio takes lithium acetate, ferric sulfate and ammonium hydrogen phosphate to be dissolved in
In ionized water, above-mentioned cobalt acid lithium particle and monoethanolamine is then added, final cobalt acid lithium: LiFePO4: mole of monoethanolamine
Than for 1:0.3:0.2, mechanical stirring 6h obtains uniform mixture under 200 turns/min.Mixture 15h is handled at 60 DEG C, is filtered
120 DEG C of vacuum drying after paper filtering, obtain jel product, and ball mill grinding 10h under further 500 turns/min obtains powder in nitrogen
1400 DEG C of sintering 1h are raised to the rate of 6 DEG C/min in gas, cooled to room temperature obtains combination electrode material.
Conductive cladding processing: the chloroform soln 100ml for the poly-triphenylamine that compound concentration is 4.5% is added appropriate multiple
Composite electrode material is allowed to be then 50:1 is filtered at 40 DEG C, stir process 2h under 100 turns/min with the mass ratio of poly-triphenylamine
Paper misgivings, 150 DEG C of dryings obtain combination electrode material of the present invention further across the ball-milling treatment 72h of 300 turns/min.
(2) electrode material performance test:
Scanning electron microscope test result: about 0.55 μm of the stratum nucleare diameter of composite material, about 0.2 μm of shell thickness, whole grain
About 1 μm of diameter, specific surface area 0.85m2/g；
Battery performance test: the material is tested with lithium piece composition half-cell, discharge voltage plateau 4.25V, 0.5C
Current density discharge capacity reaches 192mAh/g, capacity retention ratio about 85% after cycle charge-discharge 300 times under 1C electric current.
Above-described embodiment the result shows that, cobalt acid lithium is presented in cobalt acid lithium provided by the invention-iron phosphate compound anode material of lithium
It is the core-shell structure of shell for core, LiFePO4, there are the characteristics such as high capacity, high voltage and high security, in new energy with next
For having a good application prospect in lithium battery.Of the invention preparation is simple, is easy to be mass produced, and at low cost
It is honest and clean, it is environmental-friendly.
Embodiments of the present invention above described embodiment only expresses, the description thereof is more specific and detailed, but can not
Therefore limitations on the scope of the patent of the present invention are interpreted as, as long as skill obtained in the form of equivalent substitutions or equivalent transformations
Art scheme should all be fallen within the scope and spirit of the invention.
Claims (10)
1. a kind of positive electrode for battery material, the positive electrode include core-shell structure, which is characterized in that in the core-shell structure
Stratum nucleare includes cobalt acid lithium, and shell includes LiFePO4.
2. positive electrode according to claim 1, which is characterized in that the positive electrode further includes following 1) -8) it is described
At least one of:
1) diameter of stratum nucleare includes 0.5~10 μm；
2) thickness of shell includes 0.2~5 μm；
3) average grain diameter of the positive electrode includes 0.7~15 μm；
4) specific surface area of the positive electrode includes 0.25~0.85m2/g；
5) discharge voltage plateau of the positive electrode is 3.2~4.2V；
6) the 0.5C current density discharge capacity of the positive electrode includes 160~270mAh/g；
7) preparation method of the stratum nucleare includes: that cobalt salt and alkaline solution are prepared into ball shaped hydroxy oxidation using hydro-thermal reaction method
Cobalt；Gained spherical hydroxy cobalt oxide is placed in lithium hydroxide aqueous solution, makes hydrogen in lithium ion displacement hydroxy cobalt oxide to obtain the final product
Cobalt acid lithium；
8) preparation method of the shell includes: that the compound respectively containing lithium, iron and/or phosphorus is dissolved in powder containing cobalt acid lithium
Deionized water in, compound containing lithium, iron and/or phosphorus generates LiFePO4 respectively, and complexing agent is added, and heating stirring simultaneously surpasses
Sonicated obtains jel product, and dry, ball mill grinding obtains powder, roasts and/or is sintered powder in an inert atmosphere and be
Obtain electrode material granules.
3. positive electrode according to claim 2, which is characterized in that the positive electrode further includes following 1) -10) it is described
At least one of:
1) preparation method of the stratum nucleare further include: by the cobalt acid lithium being prepared filtering, drying；
2) cobalt salt includes cobalt chloride, cobalt acetate and/or cobalt nitrate；
3) alkaline solution includes sodium hydroxide solution, potassium hydroxide solution and/or sodium carbonate liquor；
4) mass ratio of the hydroxy cobalt oxide and lithium hydroxide includes 5~10:1；
5) complexing agent includes monoethanolamine, diethanol amine, tartaric acid and/or citric acid；
6) in the preparation method of the shell, cobalt acid lithium: LiFePO4: the molar ratio of complexing agent includes 1:0.05~0.5:0.01
~0.2；
7) temperature of the roasting and/or sintering includes 550 DEG C~1400 DEG C；
8) inert atmosphere includes nitrogen atmosphere；
9) molar ratio and LiFePO of the compound respectively containing lithium, iron and/or phosphorus4In lithium, iron and phosphate radical mole
Than consistent；
10) preparation method of the shell further includes conductive cladding processing: dispersing poly-triphenylamine powder in chloroform and obtains
Then the electrode material granules are dispersed in the conducting function treatment fluid by conducting function treatment fluid, stirring, is done filtering
Dry, ball mill grinding is to get positive electrode；
Specifically, the mass concentration of the conducting function treatment fluid includes 1.5%~4.5%；
And/or specifically, the mass ratio of the electrode material granules and poly-triphenylamine includes 20~50:1.
4. a kind of preparation method of positive electrode for battery material, the positive electrode includes core-shell structure, which is characterized in that the core
Stratum nucleare in shell structure includes cobalt acid lithium, and shell includes LiFePO4, the preparation method of the positive electrode include it is following 1) and/
Or 2):
1) preparation method of the stratum nucleare includes: that cobalt salt and alkaline solution are prepared into ball shaped hydroxy oxidation using hydro-thermal reaction method
Cobalt；Gained spherical hydroxy cobalt oxide is placed in lithium hydroxide aqueous solution, makes hydrogen in lithium ion displacement hydroxy cobalt oxide to obtain the final product
Cobalt acid lithium；
2) preparation method of the shell includes: and is dissolved in the compound respectively containing lithium, iron and/or phosphorus to go containing cobalt acid lithium
In ionized water, the compound containing lithium, iron and/or phosphorus generates LiFePO4 respectively, and complexing agent, heating stirring and ultrasonic wave is added
Processing obtains jel product, and dry, ball mill grinding obtains powder, roasts and/or be sintered powder in an inert atmosphere up to electricity
Pole material granule.
5. according to the method described in claim 4, it is characterized in that, the method also includes following 1) -16) it is described at least
It is a kind of:
1) preparation method of the stratum nucleare further include: by the cobalt acid lithium being prepared filtering, drying；
2) cobalt salt includes cobalt chloride, cobalt acetate and/or cobalt nitrate；
3) alkaline solution includes sodium hydroxide solution, potassium hydroxide solution and/or sodium carbonate liquor；
4) mass ratio of the hydroxy cobalt oxide and lithium hydroxide includes 5~10:1；
5) complexing agent includes monoethanolamine, diethanol amine, tartaric acid and/or citric acid；
6) in the preparation method of the shell, cobalt acid lithium: LiFePO4: the molar ratio of complexing agent includes 1:0.05~0.5:0.01
~0.2；
7) temperature of the roasting and/or sintering includes 550 DEG C~1400 DEG C；
8) inert atmosphere includes nitrogen atmosphere；
9) molar ratio and LiFePO of the compound respectively containing lithium, iron and/or phosphorus4In lithium, iron and phosphate radical mole
Than consistent；
10) preparation method of the shell further includes conductive cladding processing: dispersing poly-triphenylamine powder in chloroform and obtains
Then the electrode material granules are dispersed in the conducting function treatment fluid by conducting function treatment fluid, stirring, is done filtering
Dry, ball mill grinding is to get positive electrode；
Specifically, the mass concentration of the conducting function treatment fluid includes 1.5%~4.5%；And/or the specifically, electricity
The mass ratio of pole material granule and poly-triphenylamine includes 20~50:1；
11) diameter of stratum nucleare includes 0.5~10 μm；
12) thickness of shell includes 0.2~5 μm；
13) average grain diameter of the positive electrode includes 0.7~15 μm；
14) specific surface area of the positive electrode includes 0.25~0.85m2/g；
15) discharge voltage plateau of the positive electrode is 3.2~4.2V；
16) the 0.5C current density discharge capacity of the positive electrode includes 160~270mAh/g.
6. the positive electrode that claim 4 and/or 5 any the methods are directly prepared.
7. the application of claim 1,2,3 and/or 6 any positive electrodes, claim 4 and/or 5 any the methods.
8. application according to claim 7, which is characterized in that the application includes being used to prepare lithium battery and/or its phase
Close product.
At least one of 9. a kind of lithium battery, which is characterized in that the lithium battery includes following 1) -2) described:
1) claim 1,2,3 and/or 6 any positive electrodes；
2) preparation method includes: that claim 1,2,3 and/or 6 any positive electrodes are assembled into lithium battery.
10. a kind of preparation method of lithium battery, which is characterized in that the method includes claim 1,2,3 and/or 6 are any
The positive electrode is assembled into lithium battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910149583.7A CN109860570A (en) | 2019-02-28 | 2019-02-28 | A kind of cobalt acid lithium-iron phosphate compound anode material of lithium and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910149583.7A CN109860570A (en) | 2019-02-28 | 2019-02-28 | A kind of cobalt acid lithium-iron phosphate compound anode material of lithium and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109860570A true CN109860570A (en) | 2019-06-07 |
Family
ID=66899442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910149583.7A Withdrawn CN109860570A (en) | 2019-02-28 | 2019-02-28 | A kind of cobalt acid lithium-iron phosphate compound anode material of lithium and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109860570A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110690428A (en) * | 2019-10-12 | 2020-01-14 | 洛阳超特电源科技有限公司 | High-rate lithium iron phosphate composite material, positive pole piece and lithium ion battery |
| CN113555537A (en) * | 2021-06-11 | 2021-10-26 | 惠州锂威新能源科技有限公司 | Positive electrode material and preparation method thereof, positive plate and lithium ion battery |
| CN113860280A (en) * | 2021-09-24 | 2021-12-31 | 惠州亿纬锂能股份有限公司 | Lithium manganese iron phosphate cathode material and preparation method and application thereof |
-
2019
- 2019-02-28 CN CN201910149583.7A patent/CN109860570A/en not_active Withdrawn
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110690428A (en) * | 2019-10-12 | 2020-01-14 | 洛阳超特电源科技有限公司 | High-rate lithium iron phosphate composite material, positive pole piece and lithium ion battery |
| CN113555537A (en) * | 2021-06-11 | 2021-10-26 | 惠州锂威新能源科技有限公司 | Positive electrode material and preparation method thereof, positive plate and lithium ion battery |
| CN113555537B (en) * | 2021-06-11 | 2024-02-23 | 惠州锂威新能源科技有限公司 | Positive electrode material, preparation method thereof, positive electrode plate and lithium ion battery |
| CN113860280A (en) * | 2021-09-24 | 2021-12-31 | 惠州亿纬锂能股份有限公司 | Lithium manganese iron phosphate cathode material and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103606674B (en) | Cobalt acid lithium material of a kind of surface modification treatment and preparation method thereof | |
| CN111564605A (en) | Layered oxide positive electrode, preparation method and application thereof, and sodium ion battery containing layered oxide positive electrode | |
| EP3319152A1 (en) | Doped conductive oxide and improved electrochemical energy storage device polar plate based on same | |
| CN113929069B (en) | Manganese-rich phosphate positive electrode material and preparation method and application thereof | |
| CN106784726B (en) | Lithium vanadyl phosphate modified lithium-rich manganese-based layered lithium ion battery cathode material and preparation method thereof | |
| CN109860570A (en) | A kind of cobalt acid lithium-iron phosphate compound anode material of lithium and preparation method thereof | |
| CN101436667A (en) | Anode polyporous material of lithium ion cell and preparation method thereof | |
| CN101150191A (en) | Anode material lanthanum or Ac adulterated LiFePO4 of lithium ion secondary battery and its making method | |
| CN111162256A (en) | Mixed polyanion type sodium ion battery positive electrode material and preparation thereof | |
| CN111180709A (en) | Carbon nano tube and metal copper co-doped ferrous oxalate lithium battery composite negative electrode material and preparation method thereof | |
| EP4276947A1 (en) | Preparation method for lithium iron phosphate coated with ferroboron alloy | |
| CN102299332A (en) | Preparation method of porous lithium vanadium phosphate/carbon cathode material of lithium ion battery | |
| CN112467139A (en) | Lithium ion battery positive electrode pre-lithiation agent and preparation method and application thereof | |
| CN110085854B (en) | Lithium vanadium phosphate cathode material and preparation method thereof | |
| CN115863631A (en) | Phosphate anode material and preparation method and application thereof | |
| CN111933904A (en) | Bimetal sulfide and preparation method thereof, compound and preparation method thereof, lithium-sulfur positive electrode material and lithium-sulfur battery | |
| CN114005987B (en) | Additive for positive electrode material of sodium ion battery and positive electrode material of sodium ion battery | |
| CN110690446A (en) | Preparation method of carbon-coated ferroferric oxide for iron-nickel battery | |
| CN110085862A (en) | A kind of sode cell electrode material Na1+xFexTi2-x(PO4)3And its preparation method and application | |
| CN112777611B (en) | Rhombohedral phase Prussian blue derivative and preparation method and application thereof | |
| CN107093726A (en) | A kind of method for improving lithium ion battery electrode material chemical property | |
| CN107204464A (en) | A kind of preparation method of nano-carbon coated manganese fluorophosphate sodium and solvent-thermal method | |
| CN108807971B (en) | Lithium-rich manganese-based positive electrode material of lithium ion battery and preparation method thereof | |
| CN116344763A (en) | Metal/carbon coated lithium oxide composite positive electrode material, preparation method thereof, positive electrode plate containing positive electrode material and battery | |
| CN110943220A (en) | Lithium ion power battery composite positive electrode material 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 | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190607 |
|
| WW01 | Invention patent application withdrawn after publication |