CN106058204A - Negative pole material of lithium iron phosphate power battery and preparation method of negative pole material - Google Patents
Negative pole material of lithium iron phosphate power battery and preparation method of negative pole material Download PDFInfo
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- CN106058204A CN106058204A CN201610623535.3A CN201610623535A CN106058204A CN 106058204 A CN106058204 A CN 106058204A CN 201610623535 A CN201610623535 A CN 201610623535A CN 106058204 A CN106058204 A CN 106058204A
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
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- H01M4/00—Electrodes
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2220/00—Batteries for particular applications
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Abstract
The invention provides a negative pole material of a lithium iron phosphate power battery and a preparation method of the negative pole material. The negative pole material of the lithium iron phosphate power battery has a core-shell structure, of which petroleum coke serves as a core and carbon serves as a shell. According to the core-shell-structured negative pole material of the lithium iron phosphate power battery, provided by the invention, the petroleum coke has relatively high adaptability to various electrolytes and is relatively good in overcharging and overdischarging performance and relatively high in safety, and a charging and discharging potential curve of the petroleum coke is free of a platform (the charging and discharging potential curve is of a slope in the range of 0V to 1.2V), so that the condition of attenuation of capacity of the power battery can be very conveniently monitored according to voltage changes; the electric potential of the petroleum coke is higher than that of lithium, so that the deposition of lithium metal on a negative pole can be avoided. In addition, by taking the petroleum coke as the core and taking the carbon as the shell, the petroleum coke can be effectively prevented from volume expansion during lithium inserting, and thus the shortening of the life of the power battery is effectively prevented.
Description
Technical field
The present invention relates to electrokinetic cell field, more particularly, to a kind of lithium iron phosphate dynamic battery negative material, and should
The preparation method of lithium iron phosphate dynamic battery negative material.
Background technology
Lithium iron phosphate dynamic battery refers to LiFePO4 (LiFePO4) as the lithium ion battery of positive electrode.Due to
LiFePO4 has high energy density, cheap price, the advantage of excellent safety so that ferric phosphate lithium cell is the suitableeest
Share in electrokinetic cell field, it is widely used in hybrid vehicle, electric tool, electric bicycle, electric boosted
The every field such as car, generating and energy storage device.
Negative material is one of critical material of lithium ion battery, and carbonaceous material is people's early start studies and apply
In the material of lithium ion battery negative, the most still receive significant attention.Carbonaceous material mainly has the advantage that specific capacity is high
(200～400mAh/g), low (< the 1.0V VS Li of electrode potential+/ Li), high (> 95% of cycle efficieny), have extended cycle life.
The most more common lithium iron phosphate dynamic battery negative material includes graphite and MCMB (MCMB) etc., its
In, the large current density power of graphite is low, and power performance is poor, and MCMB has the cycle performance of excellence, but compares
Capacity is the highest, and cycle efficieny is on the low side first, and, the embedding de-lithium current potential of both negative materials is at 0-0.2V, it is easy to gold occurs
Belonging to the deposition of lithium, the safety under big current condition is poor.Additionally, graphite and MCMB negative material all have preferably
Voltage platform, although this is an advantage for small-scale lithium ion cell, but, for lithium iron phosphate dynamic battery but
It it is a shortcoming.Because the positive pole of lithium iron phosphate dynamic battery is at the discharging voltage balance of 3.2V, if using discharge voltage to put down again
Steady negative material, although whole battery system discharging voltage balance, but but cannot hold according to the variation monitoring battery of voltage
The change of amount, if the consumption of battery capacity cannot be monitored, it will causes the very big inconvenience in use.
Summary of the invention
It is an object of the present invention to provide lithium iron phosphate dynamic battery negative material, to reduce lithium metal at LiFePO4
The deposition of power battery cathode, and the decay of the battery capacity of convenient monitoring lithium iron phosphate dynamic battery.
According to an aspect of the invention, it is provided a kind of lithium iron phosphate dynamic battery negative material, have with petroleum coke
For core, the nucleocapsid structure with carbon as shell.
Optionally, described petroleum coke is that modified petroleum is burnt.
Optionally, the thickness of described shell is the 0.5%-2% of particle diameter of described nucleocapsid structure.
It is a further object to provide the preparation method of a kind of lithium iron phosphate dynamic battery negative material, to prepare
A kind of lithium metal deposition at lithium iron phosphate dynamic battery negative pole that effectively reduces, and the battery appearance of lithium iron phosphate dynamic battery
The decay of amount monitors convenient lithium iron phosphate dynamic battery negative material.
According to the second aspect of the invention, it is provided that the preparation method of a kind of lithium iron phosphate dynamic battery negative material, bag
Include following steps:
(1) filter out the particle diameter granule less than 16 mesh after being pulverized by petroleum coke, described granule is mixed with binding agent laggard
Row pelletize processes, and obtains the petroleum coke pelletize again that particle diameter is 10mm-100mm；
(2) the petroleum coke pelletize again in described step (1) is carried out heat treatment at 500 DEG C-800 DEG C, obtain forging rear stone
Oil coke；
(3) under an inert atmosphere with 6 DEG C/min-12 DEG C/min's after the after-smithing petroleum coke in described step (2) being cooled down
Heating rate is warming up to 2000 DEG C-2700 DEG C and is incubated a period of time, obtains graphitization petroleum coke；
(4) after the graphitization petroleum coke in described step (3) being mixed homogeneously with carbon source at a temperature of 150 DEG C-250 DEG C
Reaction 5h-12h, i.e. obtains lithium iron phosphate dynamic battery negative material.
Optionally, the particle diameter of the granule in described step (1) is 20 mesh-50 mesh, and described binding agent is Colophonium, described
Grain is 15:1-20:1 with the mass ratio of described binding agent.
Optionally, the heat treatment in described step (2) is carried out in atmospheric environment, and the temperature of heat treatment be 600 DEG C-
700 DEG C, the time of heat treatment is 0.5h-3h.
Optionally, described step (3) is specific as follows:
After after-smithing petroleum coke in described step (2) is cooled to room temperature, it is 50ml/min-150ml/min's at flow velocity
It is warming up to 2300 DEG C-2600 DEG C with the heating rate of 8 DEG C/min-10 DEG C/min under nitrogen atmosphere and is incubated 0.5h-5h, obtaining stone
Ink fossil oil coke.
Optionally, the carbon source in described step (4) is organic carbon source, and the matter of described graphitization petroleum coke and described carbon source
Amount ratio is 10:1-30:1.
Optionally, described step (4) is specific as follows:
First carbon source is made into carbon source solution, then the graphitization petroleum coke in described step (3) is added described carbon source solution
Middle mix homogeneously, then uses hydro-thermal method to react 5h-10h at a temperature of 150 DEG C-250 DEG C, i.e. obtains LiFePO4 power current
Pond negative material.
Optionally, described carbon source is glucose, and the concentration of described carbon source solution is 0.5mol/L-3mol/L.
It was found by the inventors of the present invention that in the prior art, it is implicitly present on existing lithium iron phosphate dynamic battery negative pole
Easily deposit lithium metal, and the problem that the decay of the battery capacity of lithium iron phosphate dynamic battery cannot be monitored.Therefore, institute of the present invention
That technical assignment to be realized or the those skilled in the art of technical problem is that to be solved never expect or it is not anticipated that
Arrive, therefore the present invention is a kind of new technical scheme.
One of the present invention has technical effect that, the petroleum coke in the lithium iron phosphate dynamic battery negative material of nucleocapsid structure
Relatively strong to the adaptability of various electrolyte, overcharging resisting, over-discharge property are preferable, and safety is higher, on its charge and discharge potential curve
Without platform (in ramped shaped in the range of 0-1.2V) so that can be very easily according to the appearance of the variation monitoring electrokinetic cell of voltage
The attenuation of amount, and, the current potential of petroleum coke is higher than the current potential of lithium, can avoid lithium metal deposition on negative pole.Additionally,
With petroleum coke as core, can effectively prevent petroleum coke from volumetric expansion occurring during slotting lithium with carbon for shell, thus effectively prevent
Reduce the life-span of electrokinetic cell.
Another of the present invention has technical effect that, the preparation method of the lithium iron phosphate dynamic battery of the present invention is successively to stone
Oil coke carries out pulverizing pelletize process, heat treatment, graphitization processing and carbon cladding and processes, and is effectively increased the charge and discharge electric capacity of petroleum coke
Amount, improves cycle performance and the high rate performance of petroleum coke, prevents petroleum coke from volumetric expansion occurring during slotting lithium.
By the detailed description of the following exemplary embodiment to the present invention, further feature and the advantage thereof of the present invention will
It is made apparent from.
Detailed description of the invention
Understandable for enabling the above-mentioned purpose of invention, feature and advantage to become apparent from, below the present invention is embodied as
Mode is described in detail.
Elaborate a lot of detail in the following description so that fully understanding the present invention, but the present invention is all right
Using other to be different from alternate manner described here to implement, those skilled in the art can be without prejudice to intension of the present invention
In the case of do similar popularization, therefore the present invention is not limited by following public specific embodiment.
The lithium iron phosphate dynamic battery negative material of the present invention has with petroleum coke as core, the nucleocapsid structure with carbon as shell,
Wherein petroleum coke is preferably modified petroleum Jiao, and the thickness of shell is preferably the 0.5%-2% of the particle diameter of nucleocapsid structure, further
The thickness of the earth's crust is preferably the 0.8%-1.5% of the particle diameter of nucleocapsid structure, and above-mentioned modified petroleum Jiao can use known in the art
Method realize, the shape of above-mentioned nucleocapsid structure may preferably be near-spherical.
In the preparation method of the lithium iron phosphate dynamic battery negative material of the present invention, first petroleum coke is carried out pulverizing and make
Grain processes, and it includes petroleum coke is pulverized the screening of laggard row, and filters out the particle diameter granule less than 16 mesh, the preferably grain of granule
Footpath is 20 mesh-50 mesh, then carries out pelletize process after being mixed with binding agent by granule, and above-mentioned binding agent can be selected for Colophonium, coal tar
Or phenolic resin etc., when binding agent is Colophonium, granule and the mass ratio of binding agent are 15:1-20:1, certainly, and art technology
Personnel select the binding agent usage amount of other binding agent and correspondence neatly also dependent on actual demand, obtain particle diameter and are
The pelletize again of the petroleum coke of 10mm-100mm；
Then petroleum coke pelletize again being carried out heat treatment, it includes carrying out petroleum coke pelletize again at 500 DEG C-800 DEG C
Heat treatment, above-mentioned heat treatment is preferably carried out in atmospheric environment, and the temperature of heat treatment is preferably 600 DEG C-700 DEG C, at heat
The time of reason is preferably 0.5h-3h, obtains after-smithing petroleum coke, and the surface of after-smithing petroleum coke aoxidizes formation in heat treatment process
Micropore；
Then after-smithing petroleum coke is carried out graphitization processing, it include by after-smithing petroleum coke cool down after under an inert atmosphere with
The heating rate of 6 DEG C/min-12 DEG C/min is warming up to 2000 DEG C-2700 DEG C and is incubated a period of time, and above-mentioned inert atmosphere can be
Nitrogen or argon, the flow velocity of the most purged after-smithing petroleum coke is the nitrogen of 50ml/min-150ml/min, above-mentioned liter
Temperature speed is preferably 8 DEG C/min-10 DEG C/min, and the temperature of above-mentioned insulation is preferably 2300 DEG C-2600 DEG C, during above-mentioned insulation
Between be preferably 0.5h-5h, more preferably 0.5h-3h, obtain graphitization petroleum coke；
Finally graphitization petroleum coke is carried out carbon cladding process, after it includes mixing homogeneously graphitization petroleum coke with carbon source
Reacting 5h-12h at a temperature of 150 DEG C-250 DEG C, above-mentioned carbon source is preferably e.g. the organic carbon source of glucose or citric acid,
And the mass ratio of graphitization petroleum coke and carbon source is 10:1-30:1；In order to ensure that graphitization petroleum coke mixes with carbon source and reacts
Uniformity, first carbon source can be made into carbon source solution, then graphitization petroleum coke is added in carbon source solution, use hydro-thermal method to exist
5h-10h is reacted at a temperature of 150 DEG C-250 DEG C, and, when carbon source is glucose, the concentration of carbon source solution is preferably
0.5mol/L-3mol/L, i.e. obtains lithium iron phosphate dynamic battery negative material.
Hereinafter, lithium iron phosphate dynamic battery negative material of the present invention and preparation method thereof is done have in conjunction with specific embodiments
Body explanation.
Embodiment 1
Petroleum coke is pulverized the screening of laggard row, filters out particle diameter granule between 20 mesh-30 mesh, then by mass ratio be
The granule of 15:1 carries out pelletize process after mixing with Colophonium, obtains the petroleum coke pelletize again that particle diameter is 10mm-50mm；Then by stone
Oil coke pelletize again carries out heat treatment 1h in atmospheric environment, at 600 DEG C, obtains after-smithing petroleum coke；Then after-smithing petroleum coke is cooled down
After under the nitrogen atmosphere of 50ml/min flow velocity, be warming up to 2600 DEG C with the heating rate of 6 DEG C/min and be incubated 1h, obtain graphite
Fossil oil coke；Graphitization petroleum coke is added 0.5mol/L's by the mass ratio 10:1 finally according to graphitization petroleum coke and glucose
Mix homogeneously in glucose solution, and at a temperature of 150 DEG C, react 5h, i.e. obtain lithium iron phosphate dynamic battery negative material,
The lithium iron phosphate dynamic battery negative material prepared has with petroleum coke as core, the nucleocapsid structure with carbon as shell, and the thickness of shell
0.7-1.1% for the particle diameter of nucleocapsid structure.
For the electrical property of the lithium iron phosphate dynamic battery negative material that inspection the present embodiment prepares, move with above-mentioned LiFePO4
Power cell negative electrode material prepare electrode be negative pole, with iron phosphate lithium electrode as positive electrode prepare electrode as positive pole, with
6M potassium hydroxide solution is (containing 0.1M Na2S and 0.4M LiOH) it is electrolyte, positive and negative interpolar places polyalkene diaphragm, prepares
Lithium iron phosphate dynamic battery, carries out electrochemical property test with reference to GB GB/T18287-2000 to battery.Test result such as table 1
Shown in.
Embodiment 2
Petroleum coke is pulverized the screening of laggard row, filters out particle diameter granule between 30 mesh-40 mesh, then by mass ratio be
The granule of 20:1 carries out pelletize process after mixing with Colophonium, obtains the petroleum coke pelletize again that particle diameter is 30mm-80mm；Then by stone
Oil coke pelletize again carries out heat treatment 2h in atmospheric environment, at 700 DEG C, obtains after-smithing petroleum coke；Then after-smithing petroleum coke is cooled down
After under the nitrogen atmosphere of 100ml/min flow velocity, be warming up to 2300 DEG C with the heating rate of 10 DEG C/min and be incubated 2h, obtain stone
Ink fossil oil coke；Graphitization petroleum coke is added 1mol/L's by the mass ratio 20:1 finally according to graphitization petroleum coke and glucose
Mix homogeneously in glucose solution, and at a temperature of 200 DEG C, react 8h, i.e. obtain lithium iron phosphate dynamic battery negative material,
The lithium iron phosphate dynamic battery negative material prepared has with petroleum coke as core, the nucleocapsid structure with carbon as shell, and the thickness of shell
0.8-1.5% for the particle diameter of nucleocapsid structure.
For the electrical property of the lithium iron phosphate dynamic battery negative material that inspection the present embodiment prepares, move with above-mentioned LiFePO4
Power cell negative electrode material prepare electrode be negative pole, with iron phosphate lithium electrode as positive electrode prepare electrode as positive pole, with
6M potassium hydroxide solution is (containing 0.1M Na2S and 0.4M LiOH) it is electrolyte, positive and negative interpolar places polyalkene diaphragm, prepares
Lithium iron phosphate dynamic battery, carries out electrochemical property test with reference to GB GB/T18287-2000 to battery.Test result such as table 1
Shown in.
Embodiment 3
Petroleum coke is pulverized the screening of laggard row, filters out particle diameter granule between 40 mesh-50 mesh, then by mass ratio be
The granule of 20:1 carries out pelletize process after mixing with Colophonium, obtains the petroleum coke pelletize again that particle diameter is 50mm-100mm；Then will
Petroleum coke pelletize again carries out heat treatment 3h in atmospheric environment, at 800 DEG C, obtains after-smithing petroleum coke；Then after-smithing petroleum coke is cold
But under the nitrogen atmosphere of 150ml/min flow velocity, it is warming up to 2000 DEG C with the heating rate of 12 DEG C/min after and is incubated 3h, obtaining
Graphitization petroleum coke；Graphitization petroleum coke is added 3mol/L by the mass ratio 30:1 finally according to graphitization petroleum coke and glucose
Glucose solution in mix homogeneously, and at a temperature of 200 DEG C react 10h, i.e. obtain lithium iron phosphate dynamic battery negative pole material
Material, the lithium iron phosphate dynamic battery negative material prepared has with petroleum coke as core, the nucleocapsid structure with carbon as shell, and the thickness of shell
Degree is the 1.0-1.5% of the particle diameter of nucleocapsid structure.
For the electrical property of the lithium iron phosphate dynamic battery negative material that inspection the present embodiment prepares, move with above-mentioned LiFePO4
Power cell negative electrode material prepare electrode be negative pole, with iron phosphate lithium electrode as positive electrode prepare electrode as positive pole, with
6M potassium hydroxide solution is (containing 0.1M Na2S and 0.4M LiOH) it is electrolyte, positive and negative interpolar places polyalkene diaphragm, prepares
Lithium iron phosphate dynamic battery, carries out electrochemical property test with reference to GB GB/T18287-2000 to battery.Test result such as table 1
Shown in.
Embodiment 4
Petroleum coke is pulverized the screening of laggard row, filters out particle diameter granule between 20 mesh-40 mesh, then by mass ratio be
The granule of 18:1 carries out pelletize process after mixing with Colophonium, obtains the petroleum coke pelletize again that particle diameter is 50mm-80mm；Then by stone
Oil coke pelletize again carries out heat treatment 0.5h in atmospheric environment, at 500 DEG C, obtains after-smithing petroleum coke；Then after-smithing petroleum coke is cold
But under the nitrogen atmosphere of 100ml/min flow velocity, it is warming up to 2600 DEG C with the heating rate of 10 DEG C/min after and is incubated 4h, obtaining
Graphitization petroleum coke；Graphitization petroleum coke is added 2mol/L by the mass ratio 30:1 finally according to graphitization petroleum coke and glucose
Glucose solution in mix homogeneously, and at a temperature of 250 DEG C react 6h, i.e. obtain lithium iron phosphate dynamic battery negative pole material
Material, the lithium iron phosphate dynamic battery negative material prepared has with petroleum coke as core, the nucleocapsid structure with carbon as shell, and the thickness of shell
Degree is the 0.6-1.2% of the particle diameter of nucleocapsid structure.
For the electrical property of the lithium iron phosphate dynamic battery negative material that inspection the present embodiment prepares, move with above-mentioned LiFePO4
Power cell negative electrode material prepare electrode be negative pole, with iron phosphate lithium electrode as positive electrode prepare electrode as positive pole, with
6M potassium hydroxide solution is (containing 0.1M Na2S and 0.4M LiOH) it is electrolyte, positive and negative interpolar places polyalkene diaphragm, prepares
Lithium iron phosphate dynamic battery, carries out electrochemical property test with reference to GB GB/T18287-2000 to battery.Test result such as table 1
Shown in.
Embodiment 5
Petroleum coke is pulverized the screening of laggard row, filters out particle diameter granule between 30 mesh-40 mesh, then by mass ratio be
The granule of 15:1 carries out pelletize process after mixing with Colophonium, obtains the petroleum coke pelletize again that particle diameter is 30mm-80mm；Then by stone
Oil coke pelletize again carries out heat treatment 2h in atmospheric environment, at 700 DEG C, obtains after-smithing petroleum coke；Then after-smithing petroleum coke is cooled down
After under the nitrogen atmosphere of 100ml/min flow velocity, be warming up to 2400 DEG C with the heating rate of 9 DEG C/min and be incubated 2h, obtain graphite
Fossil oil coke；Finally according to graphitization petroleum coke and glucose mass ratio 20:1 by graphitization petroleum coke add 1mol/L Portugal
Mix homogeneously in grape sugar juice, and at a temperature of 200 DEG C, react 7h, i.e. obtain lithium iron phosphate dynamic battery negative material, system
The lithium iron phosphate dynamic battery negative material obtained has with petroleum coke as core, the nucleocapsid structure with carbon as shell, and the thickness of shell is
The 0.8-1.1% of the particle diameter of nucleocapsid structure.
For the electrical property of the lithium iron phosphate dynamic battery negative material that inspection the present embodiment prepares, move with above-mentioned LiFePO4
Power cell negative electrode material prepare electrode be negative pole, with iron phosphate lithium electrode as positive electrode prepare electrode as positive pole, with
6M potassium hydroxide solution is (containing 0.1M Na2S and 0.4M LiOH) it is electrolyte, positive and negative interpolar places polyalkene diaphragm, prepares
Lithium iron phosphate dynamic battery, carries out electrochemical property test with reference to GB GB/T18287-2000 to battery.Test result such as table
Shown in 1.
Comparative example 1
With Delanium as negative material, remaining manufacture method is same as in Example 2, the method for performance test and condition with
Embodiment 2 is identical, and test result is as shown in table 1.
Comparative example 2
With MCMB as negative material, remaining manufacture method is same as in Example 2, the method for performance test and bar
Part is same as in Example 2, and test result is as shown in table 1.
The chemical property of table 1 lithium iron phosphate dynamic battery
The iron phosphate of the lithium iron phosphate dynamic battery negative material that have employed the present invention is can be seen that by above example
Lithium dynamical battery, has good high-rate discharge ability, preferable low temperature discharge and recharge and moderate voltage platform curve.
Although by example, some specific embodiments of the present invention have been described in detail, but the skill of this area
Art personnel are it should be understood that above example is merely to illustrate rather than in order to limit the scope of the present invention.The skill of this area
Art personnel are it should be understood that can modify to above example without departing from the scope and spirit of the present invention.This
Bright scope is defined by the following claims.
Claims (10)
1. a lithium iron phosphate dynamic battery negative material, it is characterised in that have with petroleum coke as core, the nucleocapsid with carbon as shell
Structure.
Lithium iron phosphate dynamic battery negative material the most according to claim 1, it is characterised in that described petroleum coke is modified
Petroleum coke.
Lithium iron phosphate dynamic battery negative material the most according to claim 1, it is characterised in that the thickness of described shell is institute
State the 0.5%-2% of the particle diameter of nucleocapsid structure.
4. the preparation method of a lithium iron phosphate dynamic battery negative material, it is characterised in that comprise the steps:
(1) filter out the particle diameter granule less than 16 mesh after being pulverized by petroleum coke, make after described granule is mixed with binding agent
Grain processes, and obtains the petroleum coke pelletize again that particle diameter is 10mm-100mm；
(2) the petroleum coke pelletize again in described step (1) is carried out heat treatment at 500 DEG C-800 DEG C, obtain after-smithing petroleum coke；
(3) under an inert atmosphere with the intensification of 6 DEG C/min-12 DEG C/min after the after-smithing petroleum coke in described step (2) being cooled down
Ramp is to 2000 DEG C-2700 DEG C and is incubated a period of time, obtains graphitization petroleum coke；
(4) react at a temperature of 150 DEG C-250 DEG C after the graphitization petroleum coke in described step (3) being mixed homogeneously with carbon source
5h-12h, i.e. obtains lithium iron phosphate dynamic battery negative material.
Preparation method the most according to claim 4, it is characterised in that the particle diameter of the granule in described step (1) be 20 mesh-
50 mesh, described binding agent is Colophonium, and described granule is 15:1-20:1 with the mass ratio of described binding agent.
Preparation method the most according to claim 4, it is characterised in that the heat treatment in described step (2) is in atmospheric environment
In carry out, and the temperature of heat treatment is 600 DEG C-700 DEG C, and the time of heat treatment is 0.5h-3h.
Preparation method the most according to claim 4, it is characterised in that described step (3) is specific as follows:
After after-smithing petroleum coke in described step (2) is cooled to room temperature, it is the nitrogen of 50ml/min-150ml/min at flow velocity
It is warming up to 2300 DEG C-2600 DEG C with the heating rate of 8 DEG C/min-10 DEG C/min under atmosphere and is incubated 0.5h-5h, obtaining graphitization
Petroleum coke.
Preparation method the most according to claim 4, it is characterised in that the carbon source in described step (4) is organic carbon source, and
Described graphitization petroleum coke is 10:1-30:1 with the mass ratio of described carbon source.
9. according to the preparation method described in claim 4 or 8, it is characterised in that described step (4) is specific as follows:
First carbon source is made into carbon source solution, then the graphitization petroleum coke in described step (3) is added in described carbon source solution mixed
Close uniformly, then use hydro-thermal method to react 5h-10h at a temperature of 150 DEG C-250 DEG C, i.e. obtain lithium iron phosphate dynamic battery and bear
Pole material.
10. according to the preparation method described in claim 9, it is characterised in that described carbon source is glucose, described carbon source solution
Concentration be 0.5mol/L-3mol/L.
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| CN109376933A (en) * | 2018-10-30 | 2019-02-22 | 成都云材智慧数据科技有限公司 | Lithium ion battery negative material energy density prediction technique neural network based |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102050437A (en) * | 2009-10-29 | 2011-05-11 | 上海比亚迪有限公司 | Carbon composite material, and preparation method and application thereof |
| CN103325997A (en) * | 2013-06-28 | 2013-09-25 | 马树华 | Carbon material applied to negative electrode of lithium ion power battery and preparation method of carbon material |
| CN103682350A (en) * | 2013-12-25 | 2014-03-26 | 东莞市凯金新能源科技有限公司 | Preparation method of asphalt liquid phase coated modified artificial graphite lithium battery cathode material |
| US20140099546A1 (en) * | 2007-07-26 | 2014-04-10 | Lg Chem, Ltd. | Electrode active material having core-shell structure |
-
2016
- 2016-07-29 CN CN201610623535.3A patent/CN106058204A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140099546A1 (en) * | 2007-07-26 | 2014-04-10 | Lg Chem, Ltd. | Electrode active material having core-shell structure |
| CN102050437A (en) * | 2009-10-29 | 2011-05-11 | 上海比亚迪有限公司 | Carbon composite material, and preparation method and application thereof |
| CN103325997A (en) * | 2013-06-28 | 2013-09-25 | 马树华 | Carbon material applied to negative electrode of lithium ion power battery and preparation method of carbon material |
| CN103682350A (en) * | 2013-12-25 | 2014-03-26 | 东莞市凯金新能源科技有限公司 | Preparation method of asphalt liquid phase coated modified artificial graphite lithium battery cathode material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109376933A (en) * | 2018-10-30 | 2019-02-22 | 成都云材智慧数据科技有限公司 | Lithium ion battery negative material energy density prediction technique neural network based |
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