CN110482541A - A kind of preparation method and application of the artificial graphite microspheres of the structure containing lar nanometric cavities - Google Patents
A kind of preparation method and application of the artificial graphite microspheres of the structure containing lar nanometric cavities Download PDFInfo
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Abstract
The invention belongs to technical field of lithium ion battery negative, and in particular to a kind of preparation method and application of the artificial graphite microspheres of the structure containing lar nanometric cavities.Present invention mainly solves existing lithium ion battery lithium storage content is low, complex process is at high cost, and performance is poor, needs additional pellet forming process, the problems such as.The present invention, it is made by following steps: (1) surfactant and inorganic nickel or nickel hydroxide or nickel oxide being dissolved in N-Methyl pyrrolidone, it is mixed with pitch is dissolved in the organic solvent dissolved with polyvinylpyrrolidone, by ultrasound, stirring and spray drying obtain doping pitch microballoon；(2) pitch microballoon pre-oxidation treatment is adulterated, is carbonized under inert atmosphere, and graphitizable high temperature is handled under an argon atmosphere, then is placed in water by stirring, filtering and drying, and the artificial graphite microspheres of the structure containing lar nanometric cavities are obtained.
Description
Technical field
The invention belongs to technical field of lithium ion battery negative, in particular to a kind of structure containing lar nanometric cavities it is artificial
The preparation method and application of graphite microspheres.
Background technique
With the continuous development of society, people have higher requirement and phase to mobile power source especially lithium ion battery
It hopes, it is desirable to which capacity is bigger, and coulombic efficiency is higher, and high rate performance is more preferable, longer life expectancy, and it is desirable that cost further decreases.Electricity
The raising of pond performance is dependent on the development of electrode material and perfect.Therefore for a long time, lithium ion battery negative material is improved
Specific capacity reduces irreversible capacity for the first time, improves coulombic efficiency, improves high rate performance, improves circulation safe performance, uses simultaneously
The raw material and technique of low cost, are always the emphasis of negative electrode material research.
In all lithium ion battery negative materials, natural graphite has lower discharge platform, and its is low in cost, resource
It is abundant.But its structure is layer structure, easily causes the total insertion of solvent molecule, removes its synusia in charge and discharge process, leads
Send a telegraph pond poor circulation, poor safety performance.The modified natural obtained on natural graphite basis using different method of modifying
Graphite improves a lot on solvent compatibility and circulation safe performance, is the maximum product of occupation rate currently on the market.But hold
Amount is not high, high rate performance is poor is difficult to be changed by simple modification.
The solvent compatibility of artificial graphite is good, and circulation and high rate performance are preferable, but since there is no mention greatly very much for its specific capacity
Height, and its preparation cost is higher, does not have great advantage, occupation rate is not high in the market.It is natural such as Shenzhen Bei Terui
Graphite modified product carries out carbon coating processing after to the processing of natural flake graphite spheroidization, obtains 93% effect of coulomb for the first time
The discharge capacity of rate and 365mAh/g.The negative electrode material for the amorphous carbon coated natural graphite preparation that CN101117911A is mentioned, it is first
Secondary efficiency is 92% or more, and discharge capacity is 355mAh/g, the specific capacity of the artificial graphite microspheres of Shanghai China fir Taxodiaceae skill for the first time
Only 280~350mAh/g can not break through theoretical capacity, it is seen that want to obtain higher capacity not being not that single modification can be accomplished
's.
Silicon-carbon cathode with high capacity has significant progress at present, has minimal amount of product and enters market, and
The capacity of most of product only has 400~550mAh/g, but with high costs, and there are problems for batch stability, limits theirs
Commercial applications.
CN102867945B patent " the preparation side containing hollow carbon nano-structured graphite negative material of lithium ion battery
Method " in propose preparation containing hollow carbon nano-structured artificial graphite as cathode, lithium storage content, multiplying power and cycle performance obtain
It significantly improves, but needs hot-press arrangement in preparation process, limit the extensive use of this method, how to obtain lithium storage content height,
Coulombic efficiency is high, good cycle, and the good negative electrode material of high rate performance is the key that improve one of performance of lithium ion battery, forms
Whether this is cheap, the whether simple and easy measurement standard that whether can be applied as material with large-scale commercial of technique.Come at present
It says, there are no better materials come the needs of meeting future to heavy-duty battery.A kind of lithium-ion electric of CN105000545B patent
Pond artificial graphite/coke negative electrode material preparation method, further simplifies technique, does not need heat pressing process processing, same to obtain
To the artificial graphite material of better performances.However these materials be not it is spherical, be unfavorable for improve material bulk density and
Tap density.
Summary of the invention
Low for existing lithium ion battery lithium storage content, complex process is at high cost, and performance is poor, needs additional pelletizing work
Skill, the problems such as the present invention provides the preparation methods and application of a kind of artificial graphite microspheres of structure containing lar nanometric cavities.
In order to achieve the above object, present invention employs following technical proposals:
A kind of artificial graphite microspheres of the structure containing lar nanometric cavities are made by following steps:
(1) surfactant and inorganic nickel are successively dissolved in N-Methyl pyrrolidone, obtain solution A 1, or by hydrogen-oxygen
The nano particle ultrasonic disperse of change nickel or nickel oxide obtains solution A 2 into the N-Methyl pyrrolidone dissolved with surfactant,
Or surfactant and inorganic nickel is soluble in water, the aqueous solution of sodium bicarbonate is stirred and continuously added for the first time, is then added
N-Methyl pyrrolidone is again stirring for, and distillation water outlet obtains solution A 3；Pitch is dissolved in having dissolved with polyvinylpyrrolidone
In solvent, solution B is obtained；Solution A 1 or A2 or A3 and solution B are mixed；By ultrasound, stirring and spray drying, one-step method
Partial size is obtained in 0.5~10 μm of the doping pitch microballoon containing inorganic nickel doping or mixing containing metal nanoparticle doping
Miscellaneous pitch microballoon or the doping pitch microballoon of the hydroxide nanoparticles doping containing nickel；
(2) by containing inorganic nickel adulterate doping pitch microballoon or containing metal nanoparticle doping doping pitch it is micro-
Ball or the doping pitch microballoon of the hydroxide nanoparticles doping containing nickel carry out pre-oxidation treatment, inertia in air atmosphere
Charing process is carried out under atmosphere and obtains coke microballoon, and by coke microballoon, graphitizable high temperature handles to obtain artificial stone under an argon atmosphere
Black microballoon；Artificial graphite microspheres are placed in water by stirring, filtering and drying, removal surfactant is obtained and are existed with nickel salt
The artificial graphite microspheres of inorganic salts produced during the preparation process, the as artificial graphite microspheres of the structure containing lar nanometric cavities.
Surfactant in the step (1) are as follows: cationic surfactant, anionic surfactant or nonionic
Surfactant；The inorganic nickel are as follows: nickel nitrate, nickel chloride, nickel sulfate or nickel oxalate；The surfactant with it is inorganic
The mass ratio of nickel salt is 1: 1-5, and the surfactant is 1: 1-20 with the mass ratio of nickel hydroxide or nickel oxide nanoparticle；
The mass ratio of the inorganic nickel and pitch is 1: 2-20, the mass ratio of the nickel hydroxide or nickel oxide nanoparticle and pitch
It is 1: 2-20；The mass ratio of the N-Methyl pyrrolidone and surfactant and inorganic nickel are as follows: 100mL:0.1~5g:0.1
~25g；
The ratio of the inorganic nickel and sodium bicarbonate, by nickel and sodium bicarbonate molar ratio be 1:2 be added, temperature be 20~
30℃；Described to stir for the first time: mixing time is 2~5h, described to be again stirring for: mixing time 1h；
The pitch be the isotropic pitch modulated by raw material of coal tar, ethylene bottom oil, petroleum residual oil or naphthalene,
Anisotropic pitch or mesophase pitch, softening point are 100~280 DEG C；The quality of the pitch and polyvinylpyrrolidone
Than for 1:0.01~0.5；
The organic solvent is N-Methyl pyrrolidone, benzene, toluene, tetrahydrofuran, quinoline or pyridine；The pitch with have
The mass volume ratio of solvent is 1~100mg/mL；The process conditions of the spray drying are as follows: 140-250 DEG C of inlet temperature goes out
100-180 DEG C of temperature of mouth.
The condition of charing process in the step (2) are as follows: carbonization temperature is 600~900 DEG C, and carbonization time is 1~6h；Institute
State the condition of graphitization processing are as follows: graphitization temperature is 2700~3100 DEG C；The drying process condition are as follows: drying temperature 60-
120 DEG C, drying time 5-24h.
Surfactant in the step (1) are as follows: cationic surfactant is cetyl trimethylammonium bromide；Institute
Stating anionic surfactant is neopelex；The nonionic surfactant is polyvinylpyrrolidone, institute
It is one or more of above-mentioned with surfactant.
A kind of preparation method of the artificial graphite microspheres of the structure containing lar nanometric cavities, includes the following steps:
(1) surfactant and inorganic nickel are successively dissolved in N-Methyl pyrrolidone, obtain solution A 1, or by hydrogen-oxygen
The nano particle ultrasonic disperse of change nickel or nickel oxide obtains solution A 2 into the N-Methyl pyrrolidone dissolved with surfactant,
Or surfactant and inorganic nickel is soluble in water, the aqueous solution of sodium bicarbonate is stirred and continuously added for the first time, is then added
N-Methyl pyrrolidone is again stirring for, and distillation water outlet obtains solution A 3；Pitch is dissolved in having dissolved with polyvinylpyrrolidone
In solvent, solution B is obtained；Solution A 1 or A2 or A3 and solution B are mixed；By ultrasound, stirring and spray drying, one-step method
Partial size is obtained in 0.5~10 μm of the doping pitch microballoon containing inorganic nickel doping or mixing containing metal nanoparticle doping
Miscellaneous pitch microballoon or the doping pitch microballoon of the hydroxide nanoparticles doping containing nickel；
(2) by containing inorganic nickel adulterate doping pitch microballoon or containing metal nanoparticle doping doping pitch it is micro-
Ball or the doping pitch microballoon of the hydroxide nanoparticles doping containing nickel carry out pre-oxidation treatment, inertia in air atmosphere
Charing process is carried out under atmosphere and obtains coke microballoon, and by coke microballoon, graphitizable high temperature handles to obtain artificial stone under an argon atmosphere
Black microballoon；Artificial graphite microspheres are placed in water by stirring, filtering and drying, removal surfactant is obtained and are existed with nickel salt
The artificial graphite microspheres of inorganic salts produced during the preparation process, the as artificial graphite microspheres of the structure containing lar nanometric cavities.
Surfactant in the step (1) are as follows: cationic surfactant, anionic surfactant or nonionic
Surfactant；The inorganic nickel are as follows: nickel chloride, nickel sulfate, nickel oxalate or nickel nitrate；The surfactant with it is inorganic
The mass ratio of nickel salt is 1: 1-5, and the surfactant is 1: 1-20 with the mass ratio of nickel hydroxide or nickel oxide nanoparticle；
The mass ratio of the inorganic nickel and pitch is 1: 2-20, the mass ratio of the nickel hydroxide or nickel oxide nanoparticle and pitch
It is 1: 2-20；The mass ratio of the N-Methyl pyrrolidone and surfactant and inorganic nickel are as follows: 100mL:0.1~5g:0.1
~25g；
The ratio of the inorganic nickel and sodium bicarbonate, by nickel and sodium bicarbonate molar ratio be 1:2 be added, temperature be 20~
30℃；Described to stir for the first time: mixing time is 2~5h, described to be again stirring for: mixing time 1h；
The pitch be the isotropic pitch modulated by raw material of coal tar, ethylene bottom oil, petroleum residual oil or naphthalene,
Anisotropic pitch or mesophase pitch, softening point are 100~280 DEG C；The quality of the pitch and polyvinylpyrrolidone
Than for 1:0.01~0.5；The organic solvent is N-Methyl pyrrolidone, benzene, toluene, tetrahydrofuran, quinoline or pyridine；It is described
The mass volume ratio of pitch and organic solvent is 1~100mg/mL；The process conditions of the spray drying are as follows: inlet temperature 140-
250 DEG C, 100-180 DEG C of outlet temperature.
The condition of charing process in the step (2) are as follows: carbonization temperature is 600~900 DEG C, and carbonization time is 1~6h；Institute
State the condition of graphitization processing are as follows: graphitization temperature is 2700~3100 DEG C；The drying process condition are as follows: drying temperature 60-
120 DEG C, drying time 5-24h.
Surfactant in the step (1) are as follows: cationic surfactant is cetyl trimethylammonium bromide；Institute
Stating anionic surfactant is neopelex；The nonionic surfactant is polyvinylpyrrolidone, institute
It is one or more of above-mentioned with surfactant.
A kind of application of the artificial graphite microspheres of the structure containing lar nanometric cavities is applied to lithium ion battery negative material.
A kind of application of the artificial graphite microspheres of structure containing lar nanometric cavities prepares electricity using lithium cell cathode material
Pole piece, the specific method is as follows:
It is viscous with acetylene black conductor and Kynoar using the artificial graphite microspheres of the structure containing lar nanometric cavities as active material
Knot agent is added in N-methyl pyrrolidones in the ratio of 8:1:1, is ground, and is uniformly mixed, and is coated on copper foil, at 120 DEG C
After being dried in vacuo 12h, negative electrode tab is obtained, is to electrode with lithium piece, celgard2400 is diaphragm, molten with the lithium hexafluoro phosphate of 1M
In mass ratio be 1:1 ethylene carbonate and dimethyl carbonate mixed solvent be electrolyte, in content < 1ppm of oxygen and water
It in glove box, is placed in CR2032 button cell shell, is packaged to obtain lithium ion battery using sealing machine, and test its electrification
Learn performance.
Compared with prior art the invention has the following advantages that
The artificial graphite microspheres of lar nanometric cavities structure contained by the present invention have that solvent compatibility is good, and coulombic efficiency is high, reversible ratio
The advantages of capacity is high, and high rate performance is excellent, good cycle, the first charge discharge efficiency of the negative electrode material is 80% or more, coulomb later
Efficiency is mostly 98% or more.Bulk density and tap density are higher, and be doped nano nickel particles are more uniform to be dispersed in drip
In blueness, a series of final in-situ preparation lar nanometric cavities structure of variation can occur during heat treatment, which provides a large amount of
Lithium space and active sites are stored up, the lithium storage content of material, which has, significantly to be improved, and reaches 400mAh/g under the current density of 50mA/g
More than, the 400mAh/g or more (capacity of most of commercialized graphite cathode material at present is reached under the current density of 200mA/g
Within the scope of 280-360mAh/g), at the same material high rate performance also due to a large amount of hollow carbon nano-structured presence obtain compared with
It is big to improve, it still can reach 200-300mAh/g under the high current density of 800mA/g, can be used for conventional lithium-ion battery and power
Lithium ion battery.And the raw materials used in the present invention abundance, low in cost, manufacture craft is simple, easy to industrialized production.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the graphite microspheres of the structure containing lar nanometric cavities；
Fig. 2 is the transmission electron microscope picture of the graphite microspheres of the structure containing lar nanometric cavities；
Fig. 3 is the high rate performance figure of the graphite microspheres of the structure containing lar nanometric cavities.
Specific embodiment
Embodiment 1
A kind of artificial graphite microspheres of the structure containing lar nanometric cavities are made by following steps:
(1) cetyl trimethylammonium bromide and nickel chloride are successively dissolved in N-Methyl pyrrolidone, cetyl three
The mass ratio of methyl bromide ammonium and nickel chloride is 1: 1, obtains solution A 1, and the mass ratio of nickel chloride and pitch is 1: 2, pitch be with
Coal tar is raw material and the isotropic pitch modulated, softening point are 100 DEG C and pitch are dissolved in dissolved with polyvinylpyrrolidone
N-Methyl pyrrolidone in, the mass ratio of pitch and polyvinylpyrrolidone is 1:0.01；Pitch and N-Methyl pyrrolidone
Mass volume ratio be 1mg/mL；Obtain solution B；Solution A 1 and solution B are mixed；By ultrasound, stirring and spray drying enter
Mouth 140 DEG C of temperature, 100 DEG C of outlet temperature, one-step method obtain doping pitch containing nickel chloride doping of the partial size at 0.5~10 μm
Microballoon；
(2) the doping pitch microballoon adulterated containing nickel chloride is subjected to pre-oxidation treatment, inert atmosphere in air atmosphere
Lower progress charing process carbonization temperature is 600 DEG C, and carbonization time 6h obtains coke microballoon, by coke microballoon in argon atmosphere
Lower 2700 DEG C of graphitizable high temperatures handle to obtain artificial graphite microspheres；By artificial graphite microspheres be placed in water by stirring, filtering and
Drying for 24 hours, obtains the artificial graphite of removal surfactant and the inorganic salts generated during the preparation process with nickel chloride at 60 DEG C
Microballoon, the as artificial graphite microspheres of the structure containing lar nanometric cavities.It is micro- to the graphite of the structure manufactured in the present embodiment containing lar nanometric cavities
The scanning electron microscope (SEM) photograph of ball, is shown in Fig. 1；Artificial graphite material pattern as shown in Figure 1 is spherical shape, and partial size is at 1~5 micron.Meet existing
There is the requirement of battery producing line.Biggish bulk density not only may be implemented, also have with electrolyte and adequately contact, to protect
The excellent high rate performance of the material is hindered.The transmission electron microscope picture of the graphite microspheres of the structure containing lar nanometric cavities, is shown in Fig. 2.As shown in Figure 2
The high-resolution-ration transmission electric-lens of artificial graphite microspheres can see, which is micro- by numerous hollow structure carbon nanometers
Ball is accumulated, and cavity 2~5nm of shell thickness, 5~20nm of cavity size are that the nano nickel formed during heat treatment is urged
Bitumencarb is formed around agent catalyzed graphitization.The boiling point of nano nickel is lower than the boiling point of nickel under normal temperature and pressure, therefore in graphite
It can volatilize away during change, leave a large amount of lar nanometric cavities structures.
A kind of preparation method of the artificial graphite microspheres of the structure containing lar nanometric cavities, includes the following steps:
(1) cetyl trimethylammonium bromide and nickel chloride are successively dissolved in N-Methyl pyrrolidone, cetyl three
The mass ratio of methyl bromide ammonium and nickel chloride is 1: 1, obtains solution A 1, and the mass ratio of nickel chloride and pitch is 1: 2, pitch be with
Coal tar is raw material and the isotropic pitch modulated, softening point are 100 DEG C and pitch are dissolved in dissolved with polyvinylpyrrolidone
N-Methyl pyrrolidone in, the mass ratio of pitch and polyvinylpyrrolidone is 1:0.01；Pitch and N-Methyl pyrrolidone
Mass volume ratio be 1mg/mL；Obtain solution B；Solution A 1 and solution B are mixed；By ultrasound, stirring and spray drying enter
Mouth 140 DEG C of temperature, 100 DEG C of outlet temperature, one-step method obtain doping pitch containing nickel chloride doping of the partial size at 0.5~10 μm
Microballoon；
(2) the doping pitch microballoon adulterated containing nickel chloride is subjected to pre-oxidation treatment, inert atmosphere in air atmosphere
Lower progress charing process carbonization temperature is 600 DEG C, and carbonization time 6h obtains coke microballoon, by coke microballoon in argon atmosphere
Lower 2700 DEG C of graphitizable high temperatures handle to obtain artificial graphite microspheres；By artificial graphite microspheres be placed in water by stirring, filtering and
Drying for 24 hours, obtains the artificial graphite of removal surfactant and the inorganic salts generated during the preparation process with nickel chloride at 60 DEG C
Microballoon, the as artificial graphite microspheres of the structure containing lar nanometric cavities.
Embodiment 2
A kind of artificial graphite microspheres of the structure containing lar nanometric cavities are made by following steps:
(1) by the nano particle ultrasonic disperse of nickel hydroxide or nickel oxide to the N- methyl dissolved with neopelex
In pyrrolidones, neopelex is 1: 20 with the mass ratio of nickel hydroxide or nickel oxide nanoparticle, obtains solution
A2, pitch are the anisotropic pitch modulated using ethylene bottom oil as raw material, and softening point is 280 DEG C, nickel hydroxide or oxidation
The mass ratio of nano nickel particles and pitch is 1: 20, and pitch is dissolved in the pyridine dissolved with polyvinylpyrrolidone, pitch and poly-
The mass ratio of vinylpyrrolidone is 1:0.5, and the mass volume ratio of pitch and pyridine is 100mg/mL, obtains solution B；By solution
A2 and solution B mixing；By ultrasound, stirring and spray drying, 250 DEG C of inlet temperature, 180 DEG C of outlet temperature, one-step method is obtained
Doping pitch microballoon containing metal nanoparticle doping of the partial size at 0.5~10 μm；
(2) the doping pitch microballoon adulterated containing metal nanoparticle is subjected to pre-oxidation treatment in air atmosphere, it is lazy
Property atmosphere under carry out charing process, carbonization temperature is 900 DEG C, carbonization time 1h, coke microballoon is obtained, by coke microballoon in argon
The lower 3100 DEG C of graphitizable high temperatures of gas atmosphere handle to obtain artificial graphite microspheres；By artificial graphite microspheres be placed in water by stirring,
Dry 5h at filtering and 120 DEG C, obtain removal surfactant and the inorganic salts that are generated during the preparation process with nickel salt it is artificial
Graphite microspheres, the as artificial graphite microspheres of the structure containing lar nanometric cavities.
A kind of preparation method of the artificial graphite microspheres of the structure containing lar nanometric cavities, includes the following steps:
(1) by the nano particle ultrasonic disperse of nickel hydroxide or nickel oxide to the N- methyl dissolved with neopelex
In pyrrolidones, neopelex is 1: 20 with the mass ratio of nickel hydroxide or nickel oxide nanoparticle, obtains solution
A2, pitch are the anisotropic pitch modulated using ethylene bottom oil as raw material, and softening point is 280 DEG C, nickel hydroxide or oxidation
The mass ratio of nano nickel particles and pitch is 1: 20, and pitch is dissolved in the pyridine dissolved with polyvinylpyrrolidone, pitch and poly-
The mass ratio of vinylpyrrolidone is 1:0.5, and the mass volume ratio of pitch and pyridine is 100mg/mL, obtains solution B；By solution
A2 and solution B mixing；By ultrasound, stirring and spray drying, 250 DEG C of inlet temperature, 180 DEG C of outlet temperature, one-step method is obtained
Doping pitch microballoon containing metal nanoparticle doping of the partial size at 0.5~10 μm；
(2) the doping pitch microballoon adulterated containing metal nanoparticle is subjected to pre-oxidation treatment in air atmosphere, it is lazy
Property atmosphere under carry out charing process, carbonization temperature is 900 DEG C, carbonization time 1h, coke microballoon is obtained, by coke microballoon in argon
The lower 3100 DEG C of graphitizable high temperatures of gas atmosphere handle to obtain artificial graphite microspheres；By artificial graphite microspheres be placed in water by stirring,
Dry 5h at filtering and 120 DEG C, obtain removal surfactant and the inorganic salts that are generated during the preparation process with nickel salt it is artificial
Graphite microspheres, the as artificial graphite microspheres of the structure containing lar nanometric cavities.
Embodiment 3
A kind of artificial graphite microspheres of the structure containing lar nanometric cavities are made by following steps:
(1) polyvinylpyrrolidone and nickel sulfate is soluble in water, it stirs 3h for the first time and continuously adds the water of sodium bicarbonate
The ratio of solution, nickel sulfate and sodium bicarbonate is 1:2 addition by nickel and sodium bicarbonate molar ratio, and temperature is 25 DEG C, is then added
N-Methyl pyrrolidone is again stirring for 1h, 100 DEG C of distillation water outlets, N-Methyl pyrrolidone and polyvinylpyrrolidone and sulfuric acid
The mass ratio of nickel are as follows: 100mL:0.1g:0.1g obtains solution A 3；Pitch is the centre modulated using petroleum residual oil as raw material
Asphalt phase, softening point are 200 DEG C, and pitch is dissolved in the tetrahydrofuran dissolved with polyvinylpyrrolidone, nickel sulfate and pitch
Mass ratio is 1: 10, and the mass ratio of pitch and polyvinylpyrrolidone is 1:0.2, and the mass volume ratio of pitch and tetrahydrofuran is
50mg/mL obtains solution B；Solution A 3 and solution B are mixed；By ultrasound, stirring and spray drying, 200 DEG C of inlet temperature,
150 DEG C of outlet temperature, one-step method obtains partial size in the doping drip of 0.5~10 μm of the hydroxide nanoparticles doping containing nickel
Green microballoon；
(2) the doping pitch microballoon by the hydroxide nanoparticles doping containing nickel pre-oxidizes in air atmosphere
It handles, charing process is carried out under inert atmosphere, carbonization temperature is 800 DEG C, and carbonization time 4h obtains coke microballoon, by coke
2900 DEG C of graphitizable high temperatures handle to obtain artificial graphite microspheres microballoon under an argon atmosphere；By artificial graphite microspheres be placed in water through
Cross dry 9h at stirring, filtering and 100 DEG C, the inorganic salts for obtaining removal surfactant and generating during the preparation process with nickel salt
Artificial graphite microspheres, as artificial graphite microspheres of the structure containing lar nanometric cavities.
A kind of preparation method of the artificial graphite microspheres of the structure containing lar nanometric cavities, includes the following steps:
(1) polyvinylpyrrolidone and nickel sulfate is soluble in water, it stirs 3h for the first time and continuously adds the water of sodium bicarbonate
The ratio of solution, nickel sulfate and sodium bicarbonate is 1:2 addition by nickel and sodium bicarbonate molar ratio, and temperature is 25 DEG C, is then added
N-Methyl pyrrolidone is again stirring for 1h, 100 DEG C of distillation water outlets, N-Methyl pyrrolidone and polyvinylpyrrolidone and sulfuric acid
The mass ratio of nickel are as follows: 100mL:0.1g:0.1g obtains solution A 3；Pitch is the centre modulated using petroleum residual oil as raw material
Asphalt phase, softening point are 200 DEG C, and pitch is dissolved in the tetrahydrofuran dissolved with polyvinylpyrrolidone, nickel sulfate and pitch
Mass ratio is 1: 10, and the mass ratio of pitch and polyvinylpyrrolidone is 1:0.2, and the mass volume ratio of pitch and tetrahydrofuran is
50mg/mL obtains solution B；Solution A 3 and solution B are mixed；By ultrasound, stirring and spray drying, 200 DEG C of inlet temperature,
150 DEG C of outlet temperature, one-step method obtains partial size in the doping drip of 0.5~10 μm of the hydroxide nanoparticles doping containing nickel
Green microballoon；
(2) the doping pitch microballoon by the hydroxide nanoparticles doping containing nickel pre-oxidizes in air atmosphere
It handles, charing process is carried out under inert atmosphere, carbonization temperature is 800 DEG C, and carbonization time 4h obtains coke microballoon, by coke
2900 DEG C of graphitizable high temperatures handle to obtain artificial graphite microspheres microballoon under an argon atmosphere；By artificial graphite microspheres be placed in water through
Cross dry 9h at stirring, filtering and 100 DEG C, the inorganic salts for obtaining removal surfactant and generating during the preparation process with nickel salt
Artificial graphite microspheres, as artificial graphite microspheres of the structure containing lar nanometric cavities.
Embodiment 4
A kind of artificial graphite microspheres of the structure containing lar nanometric cavities are made by following steps:
(1) polyvinylpyrrolidone and nickel sulfate is soluble in water, it stirs 3h for the first time and continuously adds the water of sodium bicarbonate
The ratio of solution, nickel sulfate and sodium bicarbonate is 1:2 addition by nickel and sodium bicarbonate molar ratio, and temperature is 25 DEG C, is then added
N-Methyl pyrrolidone is again stirring for 1h, 100 DEG C of distillation water outlets, N-Methyl pyrrolidone and polyvinylpyrrolidone and sulfuric acid
The mass ratio of nickel are as follows: 100mL:5g:25g obtains solution A 3；Pitch is the interphase drip modulated using petroleum residual oil as raw material
Blueness, softening point are 200 DEG C, pitch are dissolved in the tetrahydrofuran dissolved with polyvinylpyrrolidone, the quality of nickel sulfate and pitch
Than being 1: 10, the mass ratio of pitch and polyvinylpyrrolidone is 1:0.2, and the mass volume ratio of pitch and tetrahydrofuran is
50mg/mL obtains solution B；Solution A 3 and solution B are mixed；By ultrasound, stirring and spray drying, 200 DEG C of inlet temperature,
150 DEG C of outlet temperature, one-step method obtains partial size in the doping drip of 0.5~10 μm of the hydroxide nanoparticles doping containing nickel
Green microballoon；
(2) the doping pitch microballoon by the hydroxide nanoparticles doping containing nickel pre-oxidizes in air atmosphere
It handles, charing process is carried out under inert atmosphere, carbonization temperature is 800 DEG C, and carbonization time 4h obtains coke microballoon, by coke
2900 DEG C of graphitizable high temperatures handle to obtain artificial graphite microspheres microballoon under an argon atmosphere；By artificial graphite microspheres be placed in water through
Cross dry 9h at stirring, filtering and 100 DEG C, the inorganic salts for obtaining removal surfactant and generating during the preparation process with nickel salt
Artificial graphite microspheres, as artificial graphite microspheres of the structure containing lar nanometric cavities.
A kind of preparation method of the artificial graphite microspheres of the structure containing lar nanometric cavities, includes the following steps:
(1) polyvinylpyrrolidone and nickel sulfate is soluble in water, it stirs 3h for the first time and continuously adds the water of sodium bicarbonate
The ratio of solution, nickel sulfate and sodium bicarbonate is 1:2 addition by nickel and sodium bicarbonate molar ratio, and temperature is 25 DEG C, is then added
N-Methyl pyrrolidone is again stirring for 1h, 100 DEG C of distillation water outlets, N-Methyl pyrrolidone and polyvinylpyrrolidone and sulfuric acid
The mass ratio of nickel are as follows: 100mL:5g:25g obtains solution A 3；Pitch is the interphase drip modulated using petroleum residual oil as raw material
Blueness, softening point are 200 DEG C, pitch are dissolved in the tetrahydrofuran dissolved with polyvinylpyrrolidone, the quality of nickel sulfate and pitch
Than being 1: 10, the mass ratio of pitch and polyvinylpyrrolidone is 1:0.2, and the mass volume ratio of pitch and tetrahydrofuran is
50mg/mL obtains solution B；Solution A 3 and solution B are mixed；By ultrasound, stirring and spray drying, 200 DEG C of inlet temperature,
150 DEG C of outlet temperature, one-step method obtains partial size in the doping drip of 0.5~10 μm of the hydroxide nanoparticles doping containing nickel
Green microballoon；
(2) the doping pitch microballoon by the hydroxide nanoparticles doping containing nickel pre-oxidizes in air atmosphere
It handles, charing process is carried out under inert atmosphere, carbonization temperature is 800 DEG C, and carbonization time 4h obtains coke microballoon, by coke
2900 DEG C of graphitizable high temperatures handle to obtain artificial graphite microspheres microballoon under an argon atmosphere；By artificial graphite microspheres be placed in water through
Cross dry 9h at stirring, filtering and 100 DEG C, the inorganic salts for obtaining removal surfactant and generating during the preparation process with nickel salt
Artificial graphite microspheres, as artificial graphite microspheres of the structure containing lar nanometric cavities.
Embodiment 5
A kind of artificial graphite microspheres of the structure containing lar nanometric cavities are made by following steps:
(1) polyvinylpyrrolidone and nickel sulfate is soluble in water, it stirs 3h for the first time and continuously adds the water of sodium bicarbonate
The ratio of solution, nickel sulfate and sodium bicarbonate is 1:2 addition by nickel and sodium bicarbonate molar ratio, and temperature is 25 DEG C, is then added
N-Methyl pyrrolidone is again stirring for 1h, 100 DEG C of distillation water outlets, N-Methyl pyrrolidone and polyvinylpyrrolidone and sulfuric acid
The mass ratio of nickel are as follows: 100mL:3g:20g obtains solution A 3；Pitch is the interphase drip modulated using petroleum residual oil as raw material
Blueness, softening point are 200 DEG C, pitch are dissolved in the tetrahydrofuran dissolved with polyvinylpyrrolidone, the quality of nickel sulfate and pitch
Than being 1: 10, the mass ratio of pitch and polyvinylpyrrolidone is 1:0.2, and the mass volume ratio of pitch and tetrahydrofuran is
50mg/mL obtains solution B；Solution A 3 and solution B are mixed；By ultrasound, stirring and spray drying, 200 DEG C of inlet temperature,
150 DEG C of outlet temperature, one-step method obtains partial size in the doping drip of 0.5~10 μm of the hydroxide nanoparticles doping containing nickel
Green microballoon；
(2) the doping pitch microballoon by the hydroxide nanoparticles doping containing nickel pre-oxidizes in air atmosphere
It handles, charing process is carried out under inert atmosphere, carbonization temperature is 800 DEG C, and carbonization time 4h obtains coke microballoon, by coke
2900 DEG C of graphitizable high temperatures handle to obtain artificial graphite microspheres microballoon under an argon atmosphere；By artificial graphite microspheres be placed in water through
Cross dry 9h at stirring, filtering and 100 DEG C, the inorganic salts for obtaining removal surfactant and generating during the preparation process with nickel salt
Artificial graphite microspheres, as artificial graphite microspheres of the structure containing lar nanometric cavities.
A kind of preparation method of the artificial graphite microspheres of the structure containing lar nanometric cavities, includes the following steps:
(1) polyvinylpyrrolidone and nickel sulfate is soluble in water, it stirs 3h for the first time and continuously adds the water of sodium bicarbonate
The ratio of solution, nickel sulfate and sodium bicarbonate is 1:2 addition by nickel and sodium bicarbonate molar ratio, and temperature is 25 DEG C, is then added
N-Methyl pyrrolidone is again stirring for 1h, 100 DEG C of distillation water outlets, N-Methyl pyrrolidone and polyvinylpyrrolidone and sulfuric acid
The mass ratio of nickel are as follows: 100mL:3g:20g obtains solution A 3；Pitch is the interphase drip modulated using petroleum residual oil as raw material
Blueness, softening point are 200 DEG C, pitch are dissolved in the tetrahydrofuran dissolved with polyvinylpyrrolidone, the quality of nickel sulfate and pitch
Than being 1: 10, the mass ratio of pitch and polyvinylpyrrolidone is 1:0.2, and the mass volume ratio of pitch and tetrahydrofuran is
50mg/mL obtains solution B；Solution A 3 and solution B are mixed；By ultrasound, stirring and spray drying, 200 DEG C of inlet temperature,
150 DEG C of outlet temperature, one-step method obtains partial size in the doping drip of 0.5~10 μm of the hydroxide nanoparticles doping containing nickel
Green microballoon；
(2) the doping pitch microballoon by the hydroxide nanoparticles doping containing nickel pre-oxidizes in air atmosphere
It handles, charing process is carried out under inert atmosphere, carbonization temperature is 800 DEG C, and carbonization time 4h obtains coke microballoon, by coke
2900 DEG C of graphitizable high temperatures handle to obtain artificial graphite microspheres microballoon under an argon atmosphere；By artificial graphite microspheres be placed in water through
Cross dry 9h at stirring, filtering and 100 DEG C, the inorganic salts for obtaining removal surfactant and generating during the preparation process with nickel salt
Artificial graphite microspheres, as artificial graphite microspheres of the structure containing lar nanometric cavities.
Embodiment 6
A kind of application of the artificial graphite microspheres of the structure containing lar nanometric cavities is applied to lithium ion battery negative material.
Electrode slice is prepared using lithium cell cathode material, the specific method is as follows:
Sample in embodiment 1 is used to press 8:1:1's with acetylene black conductor and Kynoar binder for active material
Ratio is added in N-methyl pyrrolidones, is ground, and is uniformly mixed, and is coated on copper foil, after being dried in vacuo 12h at 120 DEG C,
Negative electrode tab is obtained, is to electrode with lithium piece, celgard2400 is diaphragm, is dissolved in mass ratio with the lithium hexafluoro phosphate of 1M for 1:1's
Ethylene carbonate and dimethyl carbonate mixed solvent are that electrolyte is placed in content < 1ppm glove box of oxygen and water
In CR2032 button cell shell, it is packaged to obtain lithium ion battery using sealing machine, and test its chemical property.Containing nanometer
The high rate performance figure of the graphite microspheres of cavity structure, is shown in Fig. 3.As shown in the high rate performance of Fig. 3 material provided, with 50mA/g's
Charge and discharge under current density, reversible gram of specific capacity are stablized in 440mAh/g, in subsequent 100,200,400,800mA/g electric current
Charge and discharge under density, reversible gram of specific capacity distribution can achieve 420,395,350,250mAh/g.1600 and 3200mA/g's
The specific capacity of 120 and 65mAh/g is still distributed in charge and discharge under high current density.And it returns under the current density of 100mA/g
Charge and discharge, reversible gram of specific capacity even can achieve and stablize in 450mAh/g.Than the multiplying power of artificial graphite at present on the market
Performance is well very much.
Claims (10)
1. a kind of artificial graphite microspheres of structure containing lar nanometric cavities, it is characterised in that: be made by following steps:
(1) surfactant and inorganic nickel are successively dissolved in N-Methyl pyrrolidone, obtain solution A 1, or by nickel hydroxide
Or the nano particle ultrasonic disperse of nickel oxide obtains solution A 2 into the N-Methyl pyrrolidone dissolved with surfactant, or will
Surfactant and inorganic nickel are soluble in water, stir and continuously add the aqueous solution of sodium bicarbonate for the first time, and N- first is then added
Base pyrrolidones, is again stirring for, and distillation water outlet obtains solution A 3；Pitch is dissolved in dissolved with the organic molten of polyvinylpyrrolidone
In agent, solution B is obtained；Solution A 1 or A2 or A3 and solution B are mixed；By ultrasound, stirring and spray drying, one-step method are obtained
Doping pitch microballoon containing inorganic nickel doping of the partial size at 0.5~10 μm or the doping drip containing metal nanoparticle doping
Green microballoon or the doping pitch microballoon of the hydroxide nanoparticles doping containing nickel；
(2) by containing inorganic nickel adulterate doping pitch microballoon or containing metal nanoparticle doping doping pitch microballoon or
The doping pitch microballoon of hydroxide nanoparticles doping containing nickel carries out pre-oxidation treatment, inert atmosphere in air atmosphere
Lower progress charing process obtains coke microballoon, by coke microballoon under an argon atmosphere graphitizable high temperature handle to obtain artificial graphite it is micro-
Ball；Artificial graphite microspheres are placed in water by stirring, filtering and drying, removal surfactant is obtained and are being prepared with nickel salt
The artificial graphite microspheres of the inorganic salts generated in the process, the as artificial graphite microspheres of the structure containing lar nanometric cavities.
2. a kind of artificial graphite microspheres of structure containing lar nanometric cavities according to claim 1, it is characterised in that: the step
(1) surfactant in are as follows: cationic surfactant, anionic surfactant or nonionic surfactant；It is described
Inorganic nickel are as follows: nickel chloride, nickel sulfate, nickel oxalate or nickel nitrate；The surfactant and the mass ratio of inorganic nickel are 1
: the mass ratio of 1-5, the surfactant and nickel hydroxide or nickel oxide nanoparticle is 1: 1-20；The inorganic nickel with
The mass ratio of pitch is 1: 2-20, and the mass ratio of the nickel hydroxide or nickel oxide nanoparticle and pitch is 1: 2-20；
The mass ratio of the N-Methyl pyrrolidone and surfactant and inorganic nickel are as follows: 100mL:0.1~5g:0.1~
25g；
The ratio of the inorganic nickel and sodium bicarbonate, is 1:2 addition by nickel and sodium bicarbonate molar ratio, and temperature is 20~30
℃；Described to stir for the first time: mixing time is 2~5h, described to be again stirring for: mixing time 1h；
The pitch be the isotropic pitch modulated by raw material of coal tar, ethylene bottom oil, petroleum residual oil or naphthalene, respectively to
Anisotropic pitch or mesophase pitch, softening point are 100~280 DEG C；
The mass ratio of the pitch and polyvinylpyrrolidone is 1:0.01~0.5；
The organic solvent is N-Methyl pyrrolidone, benzene, toluene, tetrahydrofuran, quinoline or pyridine；The pitch with it is organic molten
The mass volume ratio of agent is 1~100mg/mL；
The process conditions of the spray drying are as follows: 140-250 DEG C of inlet temperature, 100-180 DEG C of outlet temperature.
3. a kind of artificial graphite microspheres of structure containing lar nanometric cavities according to claim 1, it is characterised in that: the step
(2) condition of charing process in are as follows: carbonization temperature is 600~900 DEG C, and carbonization time is 1~6h；The item of the graphitization processing
Part are as follows: graphitization temperature is 2700~3100 DEG C；The drying process condition are as follows: 60-120 DEG C of drying temperature, drying time 5-
24h。
4. a kind of artificial graphite microspheres of structure containing lar nanometric cavities according to claim 2, it is characterised in that: the step
(1) surfactant in are as follows: cationic surfactant is cetyl trimethylammonium bromide；The anion surface active
Agent is neopelex；The nonionic surfactant is polyvinylpyrrolidone, and surfactant used is upper
One or more of state.
5. a kind of preparation method of the artificial graphite microspheres of structure containing lar nanometric cavities, characterized by the following steps:
(1) surfactant and inorganic nickel are successively dissolved in N-Methyl pyrrolidone, obtain solution A 1, or by nickel hydroxide
Or the nano particle ultrasonic disperse of nickel oxide obtains solution A 2 into the N-Methyl pyrrolidone dissolved with surfactant, or will
Surfactant and inorganic nickel are soluble in water, stir and continuously add the aqueous solution of sodium bicarbonate for the first time, and N- first is then added
Base pyrrolidones, is again stirring for, and distillation water outlet obtains solution A 3；Pitch is dissolved in dissolved with the organic molten of polyvinylpyrrolidone
In agent, solution B is obtained；Solution A 1 or A2 or A3 and solution B are mixed；By ultrasound, stirring and spray drying, one-step method are obtained
Doping pitch microballoon containing inorganic nickel doping of the partial size at 0.5~10 μm or the doping drip containing metal nanoparticle doping
Green microballoon or the doping pitch microballoon of the hydroxide nanoparticles doping containing nickel；
(2) by containing inorganic nickel adulterate doping pitch microballoon or containing metal nanoparticle doping doping pitch microballoon or
The doping pitch microballoon of hydroxide nanoparticles doping containing nickel carries out pre-oxidation treatment, inert atmosphere in air atmosphere
Lower progress charing process obtains coke microballoon, by coke microballoon under an argon atmosphere graphitizable high temperature handle to obtain artificial graphite it is micro-
Ball；Artificial graphite microspheres are placed in water by stirring, filtering and drying, removal surfactant is obtained and are being prepared with nickel salt
The artificial graphite microspheres of the inorganic salts generated in the process, the as artificial graphite microspheres of the structure containing lar nanometric cavities.
6. a kind of preparation method of the artificial graphite microspheres of structure containing lar nanometric cavities according to claim 5, feature exist
In: the surfactant in the step (1) are as follows: cationic surfactant, anionic surfactant or non-ionic surface
Activating agent；The inorganic nickel are as follows: nickel chloride, nickel sulfate, nickel oxalate or nickel nitrate；The surfactant and inorganic nickel
Mass ratio be 1: 1-5, the mass ratio of the surfactant and nickel hydroxide or nickel oxide nanoparticle is 1: 1-20；It is described
The mass ratio of inorganic nickel and pitch is 1: 2-20, and the mass ratio of the nickel hydroxide or nickel oxide nanoparticle and pitch is 1:
2-20；
The mass ratio of the N-Methyl pyrrolidone and surfactant and inorganic nickel are as follows: 100mL:0.1~5g:0.1~
25g；
The ratio of the inorganic nickel and sodium bicarbonate, is 1:2 addition by nickel and sodium bicarbonate molar ratio, and temperature is 20~30
℃；Described to stir for the first time: mixing time is 2~5h, described to be again stirring for: mixing time 1h；
The pitch be the isotropic pitch modulated by raw material of coal tar, ethylene bottom oil, petroleum residual oil or naphthalene, respectively to
Anisotropic pitch or mesophase pitch, softening point are 100~280 DEG C；
The mass ratio of the pitch and polyvinylpyrrolidone is 1:0.01~0.5；
The organic solvent is N-Methyl pyrrolidone, benzene, toluene, tetrahydrofuran, quinoline or pyridine；The pitch with it is organic molten
The mass volume ratio of agent is 1~100mg/mL；
The process conditions of the spray drying are as follows: 140-250 DEG C of inlet temperature, 100-180 DEG C of outlet temperature.
7. a kind of preparation method of the artificial graphite microspheres of structure containing lar nanometric cavities according to claim 5, feature exist
In: the condition of charing process in the step (2) are as follows: carbonization temperature is 600~900 DEG C, and carbonization time is 1~6h；The stone
The condition of inkization processing are as follows: graphitization temperature is 2700~3100 DEG C；The drying process condition are as follows: drying temperature 60-120
DEG C, drying time 5-24h.
8. a kind of preparation method of the artificial graphite microspheres of structure containing lar nanometric cavities according to claim 5, feature exist
In: the surfactant in the step (1) are as follows: cationic surfactant is cetyl trimethylammonium bromide；The yin
Ionic surface active agent is neopelex；The nonionic surfactant is polyvinylpyrrolidone, table used
Face activating agent is one or more of above-mentioned.
9. a kind of application of the artificial graphite microspheres of structure containing lar nanometric cavities, it is characterised in that: be applied to negative electrode of lithium ion battery
Material.
10. a kind of application of the artificial graphite microspheres of structure containing lar nanometric cavities according to claim 9, it is characterised in that:
Electrode slice is prepared using lithium cell cathode material, the specific method is as follows:
Using the artificial graphite microspheres of the structure containing lar nanometric cavities in claim 1 as active material, with acetylene black conductor and poly-
Vinylidene binder is added in N-methyl pyrrolidones in the ratio of 8:1:1, is ground, and is uniformly mixed, and is coated on copper foil,
After being dried in vacuo 12h at 120 DEG C, negative electrode tab is obtained, is to electrode with lithium piece, celgard2400 is diaphragm, with the hexafluoro of 1M
Lithium phosphate is dissolved in the ethylene carbonate that mass ratio is 1:1 and dimethyl carbonate mixed solvent is electrolyte, in containing for oxygen and water
It in the glove box of amount < 1ppm, is placed in CR2032 button cell shell, is packaged to obtain lithium ion battery using sealing machine, and
Test its chemical property.
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