CN102231434A - Modified natural graphite material used in lithium ion battery negative electrodes, and preparation method thereof - Google Patents
Modified natural graphite material used in lithium ion battery negative electrodes, and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a modified natural graphite material used in lithium ion battery negative electrodes. With a core-shell structure, the material comprises an inner core and a shell coated on the inner-core. The inner-core is composed of natural graphite, and the shell coated on the core is composed of an inner shell and an outer shell. The inner shell is a boron-containing hard carbon layer, and the outer shell is a soft carbon layer. The boron-containing hard carbon layer is coated on natural graphite, and the soft carbon layer is coated on the boron-containing hard layer. The method has advantages of simple technology, suitability for mass production, low graphitization processing temperature, and low cost. With advantages of small specific surface area, high tap density, high first efficiency, high specific capacity, excellent cycling performance, and good rate performance, the modified natural graphite material can be applied in power batteries.
Description
Technical field
The present invention relates to a kind of lithium ion battery modified natural graphite negative material with and preparation method thereof.
Background technology
Lithium ion battery (Lithium Ion Battery is called for short LIB) is the third generation small battery after nickel-cadmium cell, Ni-MH battery.As a kind of novel chemical power source, it has outstanding advantages such as operating voltage height, specific energy is big, the discharge potential curve is steady, self discharge is little, have extended cycle life, cryogenic property is good, memoryless, pollution-free, can satisfy people to needed battery miniaturization and of portable electronics and environmentally friendly double requirements, being widely used in mobile communication, notebook computer, taking the photograph compact electronic devices such as putting all-in-one, also is the ideal source that following electric vehicle uses.
At present, generally all be to adopt carbon materials as one of lithium ion battery important component part negative material, as hard carbon, soft carbon, graphite etc.Hard charcoal is the initial used negative material of lithium ion battery, as furfural resin, phenolic resins etc., and shortcoming such as it is low to have a reversible capacity, and efficient is low first, and platform is low, but it has excellent multiplying power and cycle performance and low-temperature characteristics simultaneously; Soft carbon is the transition state carbon of a kind of amorphous carbon to graphite, as carbonizations such as coal tar pitch, petroleum asphalt, petroleum cokes, has good cycle, characteristics such as good rate capability, but capacity is low, and processing characteristics is not good.And the charge/discharge capacity of native graphite Yin Qigao, good voltage platform, aboundresources, cost is low and be widely used.But pure natural graphite has desirable layer structure, and is very responsive to electrolyte, causes solvent molecule to insert altogether when discharging and recharging easily, causes that graphite flake layer peels off, and causes the cycle performance and the poor safety performance of battery.In addition, the heavy-current discharge performance of pure natural graphite is relatively poor.
In order to improve the chemical property of native graphite, defective when overcoming pure natural graphite and being used for negative material, prior art has been done a large amount of study on the modification, wherein using maximum a kind of methods is to coat layer of material on the native graphite surface, make its formation a kind of " nucleocapsid structure ", as U.S. Pat Patent No.5908715, Chinese patent CN1304187A and Chinese patent CN1224251A etc. coat with resinae macromolecule pyrolytic carbon and handle, can stop the common insertion of solvent molecule in the electrolyte, improve high rate performance and cycle performance, but the material specific surface after the resin-coating is bigger, cause that efficient is on the low side first, irreversible capacity is big; Chinese patent CN1585172A and Chinese patent CN1624955A adopt pitch that graphite material is coated, and high temperature graphitization, have reduced the specific surface of material, effectively stoped solvent to insert altogether, improve efficient first, but its high rate performance is not good, cycle performance fails to be improved completely.
Summary of the invention
The technical problem to be solved in the present invention is a native graphite when being used for negative material, and efficient is on the low side first before the modification, and irreversible capacity is big, and cycle performance is poor, and a kind of lithium ion battery modified natural graphite negative material and preparation method thereof is provided.
Technical scheme of the present invention is: a kind of lithium ion battery modified natural graphite negative material, has nucleocapsid structure, comprise kernel and the shell that is coated on the kernel outside, described kernel is a native graphite, the shell that is coated on the kernel outside is made up of inner casing and shell, and described inner casing is the boracic hard carbon layer, and shell is soft carbon-coating, described native graphite is coated with the boracic hard carbon layer, and the boracic hard carbon layer is coated with soft carbon-coating.
Described native graphite is that fixed carbon content 〉=99.0%, particle diameter D50 are 8 ~ 25 microns class spherical natural graphite, and the quality of described boracic hard carbon layer is 1 ~ 10% of a native graphite quality, and the quality of described soft carbon-coating is 1 ~ 10% of a native graphite quality.
The preparation method of described lithium ion battery modified natural graphite negative material, its step is as follows:
(1) the hard carbon presoma is dissolved in the organic solvent, the mass ratio of hard carbon presoma and organic solvent is 1:10 ~ 100, dissolves the back fully and adds boron-containing solution, and the back that stirs adds native graphite, abundant mixing, and decompression steams solvent and water;
(2) mixture in the step (1) is warmed up to 600 ~ 1000 ℃ with 2 ~ 3 ℃/minute speed, is incubated 1 ~ 5 hour, reduce to room temperature with 2 ~ 3 ℃/minute speed again, afterwards material fragmentation is sieved, the order number of sieve is 150 ~ 300 orders;
(3) with screenings in the step (2) and the abundant mixing of soft carbon precursor; under the environment of nitrogen or argon gas atmosphere protection; speed with 2 ~ 3 ℃/minute; be warmed up to 2500 ~ 3000 ℃ and carry out graphitization; be incubated 1 ~ 5 hour, reduce to room temperature with 2 ~ 3 ℃/minute speed again, the material fragmentation after the graphitization processing is sieved; the order number of sieve is 150 ~ 300, makes lithium ion battery modified natural graphite negative material.
The preparation method of described lithium ion battery modified natural graphite negative material, hard carbon precursor in the described step (1) is at least a in phenolic resins, epoxy resin, furane resins, poly furfuryl alcohol resin, polyacrylonitrile, Kynoar, the polyphenyl phenol, and carbon content is 50% ~ 70%.
The preparation method of described lithium ion battery modified natural graphite negative material, the organic solvent in the described step (1) is ethanol, acetone, benzene, toluene, benzinum, carbon disulfide or quinoline.
The preparation method of described lithium ion battery modified natural graphite negative material, the boron-containing solution in the described step (1) is the ethanolic solution or the aqueous solution of boric acid, boron oxide, the mass concentration 1 ~ 5% of solution, the quality of boron element accounts for 0.1 ~ 8% of hard carbon layer quality.
The equipment that adopts among the preparation method of described lithium ion battery modified natural graphite negative material, described step (2) is atmosphere box type furnace, push pedal tunnel kiln, tube furnace or kiln.
The equipment that adopts among the preparation method of described lithium ion battery modified natural graphite negative material, described step (3) is acheson furnace, carbon shirt-circuiting furnace or tandem graphitizing furnace.
The preparation method of described lithium ion battery modified natural graphite negative material, the soft carbon precursor in the described step (3) is the mixture of petroleum asphalt or coal tar pitch or petroleum asphalt and coal tar pitch.
The preparation method of described lithium ion battery modified natural graphite negative material, the softening point of described petroleum asphalt or coal tar pitch is 200 ~ 290 ℃, and carbon content is 70 ~ 80%, and average grain diameter is 2 ~ 4 microns.
The invention has the beneficial effects as follows: the present invention adopts boracic hard carbon layer coated natural graphite, hard carbon is a kind of amorphous carbon material, degree of crystallinity is low, crystal face is apart from big, and good with the compatibility of electrolyte, multiplying power and cryogenic property are good, and the adding of boron element, at high temperature can catalyzed graphitization, can greatly improve the structure of hard carbon, its ordering degree is improved greatly.And the adding of boron element can reduce the required temperature of graphitization, and processing cost is reduced.The coating of adopting soft carbon afterwards is excessive for the specific area that reduces after hard carbon coats, and improves efficient first.Technology of the present invention is simple, be fit to large-scale production, the graphitization processing temperature is low, cost is low; Specific area is little, tap density is high, efficient height, specific capacity height first; Cycle performance is fabulous, high rate performance is good, can be applicable to the native graphite of electrokinetic cell.
Description of drawings
Fig. 1 is the SEM phenogram of lithium ion battery modified natural graphite negative material.
Fig. 2 is the nucleocapsid structure figure of lithium ion battery modified natural graphite negative material.
Embodiment
A kind of lithium ion battery modified natural graphite negative material, has nucleocapsid structure, comprise kernel and the shell that is coated on the kernel outside, described kernel is a native graphite, the shell that is coated on the kernel outside is made up of inner casing and shell, described inner casing is the boracic hard carbon layer, shell is soft carbon-coating, as shown in Figure 2, described native graphite 1 is coated with boracic hard carbon layer 2, and boracic hard carbon layer 2 is coated with soft carbon-coating 3, and described native graphite is 〉=99.0% for fixed carbon content, the D50 particle diameter is 8 ~ 25 microns a class spherical natural graphite, the quality of described boracic hard carbon layer is 4.8% of a native graphite quality, and the quality of described soft carbon-coating is 4.5% of a native graphite quality.
A kind of preparation method of lithium ion battery modified natural graphite negative material:
(1) gets in the stirred tank of a 5L of 1L ethanol solution adding; add 80g phenolic resins (carbon content 60%); add 500ml then and contain the ethanolic solution of 8g boric acid; after being stirred to dissolving fully; slowly add 1000g native graphite (D50=17.5 micron under the stirring condition; carbon content 99.95); be warming up to 80 ℃ of decompressions after stirring and steam ethanol, the ethanol condensation of evaporation is reclaimed, and material cooling back is taken out and placed corundum crucible; the friction top upper cover plate is in box atmosphere furnace; under protection of nitrogen gas, be warmed up to 800 ℃ by 2 ℃/minute speed, be incubated 2 hours; reduce to room temperature with 2 ℃/minute speed again, the material fragmentation after the carbonization is crossed 270 mesh sieves.Screenings and 60g petroleum asphalt powder (280 ℃ of softening points, the D50=3 micron, carbon content 75%) abundant mixing in no medium high-speed mixer, place graphite crucible to compress sealing then, in carbon shirt-circuiting furnace, be warmed up to 2500 ℃ and carry out graphitization, be incubated 1 hour, reduce to room temperature with 2 ℃/minute speed again with 3 ℃/minute speed, material fragmentation after the graphitization processing is crossed 270 mesh sieves, and screenings is the gained negative material.The surface topography of material is seen Fig. 1.
The electrochemical property test simulated battery adopts negative material of the present invention: the SBR:CMC=96:1.7:2.3(mass ratio), add appropriate amount of deionized water furnishing pulpous state, evenly be coated on the Copper Foil and negative plate was made in vacuumize in 12 hours, in being full of the glove box of argon gas, with metal lithium sheet is to electrode, electrolyte is 1MLiPF6/EC+EMC+DMC (1:1:1), barrier film is the PE/PP/PE composite membrane, be assembled into simulated battery, current density with 0.2C discharges and recharges test, voltage is tested the first charge-discharge capacity and the first charge-discharge efficiency of negative material at 0.005 ~ 2.0V.Adopt conventional production process assembling finished product battery, positive electrode is selected LiCoO2 for use, and electrolyte is 1MLiPF6/EC+EMC+DMC (1:1:1), and barrier film is the PE/PP/PE composite membrane, the high rate performance and the cycle performance of test negative material.Test result is listed in table 1.
Change the amount of the phenolic resins among the embodiment 1 into 160g, other conditions are constant.
Detection method is with embodiment 1, and test result is listed in table 1.
Change the amount of the boric acid among the embodiment 1 into 15g, other conditions are constant.
Detection method is with embodiment 1, and test result is listed in table 1.
Embodiment 4
Change the graphitization temperature among the embodiment 1 into 2800 ℃, other conditions are constant.
Detection method is with embodiment 1, and test result is listed in table 1.
Embodiment 5
Changing the native graphite among the embodiment 1 into D50 is 10 microns, the native graphite of carbon content 99.95%, and other conditions are constant.
Detection method is with embodiment 1, and test result is listed in table 1.
Embodiment 6
A kind of lithium ion battery modified natural graphite negative material, the quality of boracic hard carbon layer is 1% of a native graphite quality, and the quality of described soft carbon-coating is 1% of a native graphite quality, and all the other are with embodiment 1.
A kind of preparation method of lithium ion battery modified natural graphite negative material:
(1) gets in the stirred tank of a 5L of 1L ethanolic solution adding, add 17g phenolic resins (carbon content 60%), add 200ml then and contain the ethanolic solution of 2g boric acid, after being stirred to dissolving fully, slowly add 1000g native graphite (D50=18 micron under the stirring condition, carbon content 99.95%), be warming up to 80 ℃ of decompressions after stirring and steam ethanol, the ethanol condensation of evaporation is reclaimed;
(2) material cooling back is taken out and is placed corundum crucible, and the friction top upper cover plate is in box atmosphere furnace, under protection of nitrogen gas, be warmed up to 800 ℃ by 2 ℃/minute speed, be incubated 5 hours, reduce to room temperature with 2 ℃/minute speed again, the material fragmentation after the carbonization is crossed 250 mesh sieves;
(3) screenings and 14g petroleum asphalt powder (250 ℃ of softening points, carbon content 75%, the D50=3 micron) abundant mixing in no medium high-speed mixer, place graphite crucible to compress sealing then, in carbon shirt-circuiting furnace, be warmed up to 2500 ℃ and carry out graphitization, be incubated 2 hours, reduce to room temperature with 2 ℃/minute speed again with 3 ℃/minute speed, material fragmentation after the graphitization processing is crossed 270 mesh sieves, and screenings is the gained negative material.
Embodiment 7
A kind of lithium ion battery modified natural graphite negative material, the quality of boracic hard carbon layer is 10% of a native graphite quality, and the quality of described soft carbon-coating is 10% of a native graphite quality, and all the other are with embodiment 1.
A kind of preparation method of lithium ion battery modified natural graphite negative material:
(1) gets in the stirred tank of a 5L of 1L ethanolic solution adding, add 167g phenolic resins (carbon content 60%), add 500ml then and contain the ethanolic solution of 17g boric acid, after being stirred to dissolving fully, slowly add 1000g native graphite (D50=18 micron under the stirring condition, carbon content 99.95%), be warming up to 80 ℃ of decompressions after stirring and steam ethanol, the ethanol condensation of evaporation is reclaimed;
(2) material cooling back is taken out and is placed corundum crucible, and the friction top upper cover plate is in box atmosphere furnace, under protection of nitrogen gas, be warmed up to 800 ℃ by 2 ℃/minute speed, be incubated 5 hours, reduce to room temperature with 2 ℃/minute speed again, the material fragmentation after the carbonization is crossed 250 mesh sieves;
(3) screenings and 134g petroleum asphalt powder (250 ℃ of softening points, carbon content 75%, the D50=3 micron) abundant mixing in no medium high-speed mixer, place graphite crucible to compress sealing then, in carbon shirt-circuiting furnace, be warmed up to 2500 ℃ and carry out graphitization, be incubated 2 hours, reduce to room temperature with 2 ℃/minute speed again with 3 ℃/minute speed, material fragmentation after the graphitization processing is crossed 270 mesh sieves, and screenings is the gained negative material.
Embodiment 8
A kind of lithium ion battery modified natural graphite negative material, the quality of boracic hard carbon layer is 4.8% of a native graphite quality, and the quality of described soft carbon-coating is 4.5% of a native graphite quality, and all the other are with embodiment 1.
A kind of preparation method of lithium ion battery modified natural graphite negative material:
(1) gets in the stirred tank of a 5L of 1L quinoline solution adding, add 80g epoxy resin (carbon content 60%), add 300ml then and contain the ethanolic solution of 10g boric acid, after being stirred to dissolving fully, slowly add 1000g native graphite (D50=8 micron under the stirring condition, carbon content 99.93%), be warming up to 80 ℃ of decompressions after stirring and steam ethanol, the ethanol condensation of evaporation is reclaimed;
(2) material cooling back is taken out and is placed corundum crucible, and the friction top upper cover plate is in box atmosphere furnace, under protection of nitrogen gas, be warmed up to 700 ℃ by 2 ℃/minute speed, be incubated 5 hours, reduce to room temperature with 2 ℃/minute speed again, the material fragmentation after the carbonization is crossed 150 mesh sieves;
(3) screenings and 60g petroleum asphalt powder (240 ℃ of softening points, carbon content 75%, the D50=3 micron) abundant mixing in no medium high-speed mixer, place graphite crucible to compress sealing then, in carbon shirt-circuiting furnace, be warmed up to 3000 ℃ and carry out graphitization, be incubated 5 hours, reduce to room temperature with 2 ℃/minute speed again with 3 ℃/minute speed, material fragmentation after the graphitization processing is crossed 300 mesh sieves, and screenings is the gained negative material.
Embodiment 9
A kind of lithium ion battery modified natural graphite negative material, the quality of boracic hard carbon layer is 4% of a native graphite quality, and the quality of described soft carbon-coating is 6.4% of a native graphite quality, and all the other are with embodiment 1.
A kind of preparation method of lithium ion battery modified natural graphite negative material:
(1) gets in the stirred tank of a 5L of 1L toluene solution adding, add 80g polyacrylonitrile (carbon content 50%, add 200mL then and contain the ethanolic solution of 5g boron oxide, after being stirred to dissolving fully, slowly add 1000g native graphite (D50=25 under the stirring condition, carbon content 99.95), be warming up to 80 ℃ of decompressions after stirring and steam ethanol, the ethanol condensation of evaporation is reclaimed;
(2) material cooling back is taken out and is placed corundum crucible, and the friction top upper cover plate is in box atmosphere furnace, under protection of nitrogen gas, be warmed up to 900 ℃ by 2 ℃/minute speed, be incubated 3 hours, reduce to room temperature with 2 ℃/minute speed again, the material fragmentation after the carbonization is crossed 200 mesh sieves;
(3) screenings and 80g coal tar pitch powder (220 ℃ of softening points, carbon content 80%, the D50=4 micron) abundant mixing in no medium high-speed mixer, place graphite crucible to compress sealing then, in carbon shirt-circuiting furnace, be warmed up to 2800 ℃ and carry out graphitization, be incubated 1 hour, reduce to room temperature with 2 ℃/minute speed again with 3 ℃/minute speed, material fragmentation after the graphitization processing is crossed 280 mesh sieves, and screenings is the gained negative material.
Embodiment 10
A kind of lithium ion battery modified natural graphite negative material, the quality of boracic hard carbon layer is 4% of a native graphite quality, and the quality of described soft carbon-coating is 4.5% of a native graphite quality, and all the other are with embodiment 1.
A kind of preparation method of lithium ion battery modified natural graphite negative material:
(1) gets in the stirred tank of a 5L of 1L acetone soln adding, add 80g furane resins (carbon content 50%), add 500ml then and contain the ethanolic solution of 20g boric acid, after being stirred to dissolving fully, slowly add 1000g native graphite (D50=18 under the stirring condition, carbon content 99.95), be warming up to 80 ℃ of decompressions after stirring and steam ethanol, the ethanol condensation of evaporation is reclaimed;
(2) material cooling back is taken out and is placed corundum crucible, and the friction top upper cover plate is in box atmosphere furnace, under protection of nitrogen gas, be warmed up to 800 ℃ by 2 ℃/minute speed, be incubated 2 hours, reduce to room temperature with 2 ℃/minute speed again, the material fragmentation after the carbonization is crossed 160 mesh sieves;
(3) screenings and 60g petroleum asphalt powder (280 ℃ of softening points, the D50=3 micron) abundant mixing in no medium high-speed mixer, place graphite crucible to compress sealing then, in carbon shirt-circuiting furnace, be warmed up to 2800 ℃ and carry out graphitization with 3 ℃/minute speed, be incubated 1 hour, reduce to room temperature with 2 ℃/minute speed again, the material fragmentation after the graphitization processing is crossed 220 mesh sieves, screenings is the gained negative material.
Comparative Examples 1
Get in the stirred tank of a 5L of 1L ethanol solution adding; add 80g phenolic resins (carbon content 60%); add 500ml then and contain the ethanolic solution of 8g boric acid; after being stirred to dissolving fully; slowly add 1000g native graphite (D50=17.5 under the stirring condition; carbon content 99.95%); be warming up to 80 ℃ of decompressions after stirring and steam ethanol, the ethanol condensation of evaporation is reclaimed, and material cooling back is taken out and placed corundum crucible; the friction top upper cover plate is in box atmosphere furnace; under protection of nitrogen gas, be warmed up to 800 ℃ by 2 ℃/minute speed, be incubated 2 hours; reduce to room temperature with 2 ℃/minute speed again, the material fragmentation after the carbonization is crossed 270 mesh sieves.Screenings places graphite crucible to compress, in carbon shirt-circuiting furnace, be warmed up to 2500 ℃ and carry out graphitization, be incubated 1 hour, reduce to room temperature with 2 ℃/minute speed again with 3 ℃/minute speed, material fragmentation after the graphitization processing is crossed 270 mesh sieves, and screenings is the gained negative material.
Detection method is with embodiment 1, and test result is listed in table 1.
Comparative Examples 2
Get 1000g native graphite (D50=17.5, carbon content 99.95%) with 60g petroleum asphalt powder (280 ℃ of softening point, the D50=3 micron, carbon content 75%) abundant mixing in no medium high-speed mixer places graphite crucible to compress then, is warmed up to 2800 ℃ with 3 ℃/minute speed and carries out graphitization in carbon shirt-circuiting furnace, be incubated 1 hour, reduce to room temperature with 2 ℃/minute speed again, the material fragmentation after the graphitization processing is sieved, screenings is the gained negative material.
Detection method is with embodiment 1, and test result is listed in table 1.
Comparative Examples 3
To not add boric acid among the embodiment 1, other conditions are constant.
Detection method is with embodiment 1, and test result is listed in table 1.
Table 1 material property contrast table
| Embodiment | Specific area (m 2/g） | Discharge capacity (mAh/g) first | First charge-discharge efficiency (%) | 1C 300 times (%) that circulate |
| Implement 1 | 1.5 | 366.1 | 96.2 | 92.1 |
| Implement 2 | 3.8 | 353.3 | 92.5 | 89.3 |
| Implement 3 | 2.5 | 357.6 | 93.8 | 87.2 |
| Implement 4 | 2.6 | 358.5 | 93.4 | 87.4 |
| Implement 5 | 2.2 | 360.5 | 95.6 | 91.1 |
| Implement 6 | 5.6 | 345.8 | 89.6 | 82.1 |
| Implement 7 | 1.7 | 352.6 | 91.1 | 89.6 |
| Implement 8 | 2.4 | 359.6 | 94.4 | 89.1 |
| Implement 9 | 1.8 | 356.4 | 93.7 | 88.6 |
| Implement 10 | 2.8 | 351.2 | 92.3 | 86.1 |
| Comparative Examples 1 | 15 | 345.6 | 86.6 | 86.0 |
| Comparative Examples 2 | 1.8 | 360.6 | 94.8 | 85.1 |
| Comparative Examples 3 | 1.5 | 350.1 | 92.1 | 90.7 |
| Embodiment | 1C 1000 times (%) that circulate | High rate performance 5C/1C(%) | High rate performance 10C/1C(%) |
| Implement 1 | 87.2 | 92.8 | 89.1 |
| Implement 2 | 83.2 | 93.1 | 90.6 |
| Implement 3 | 80.6 | 89.7 | 84.6 |
| Implement 4 | 81.7 | 92.1 | 87.1 |
| Implement 5 | 82.7 | 94.5 | 92.1 |
| Implement 6 | 78.6 | 84.7 | 76.6 |
| Implement 7 | 81.7 | 86.3 | 79.6 |
| Implement 8 | 80.5 | 95.5 | 93.2 |
| Implement 9 | 82.1 | 83.1 | 78.5 |
| Implement 10 | 80.4 | 88.6 | 83.7 |
| Comparative Examples 1 | 75.1 | 92.2 | 88.3 |
| Comparative Examples 2 | 68.6 | 82.8 | 73.3 |
| Comparative Examples 3 | 86.1 | 92.4 | 87.6 |
Claims (10)
1. lithium ion battery modified natural graphite negative material, has nucleocapsid structure, comprise kernel and the shell that is coated on the kernel outside, it is characterized in that: described kernel is a native graphite, the shell that is coated on the kernel outside is made up of inner casing and shell, and described inner casing is the boracic hard carbon layer, and shell is soft carbon-coating, described native graphite is coated with the boracic hard carbon layer, and the boracic hard carbon layer is coated with soft carbon-coating.
2. lithium ion battery modified natural graphite negative material according to claim 1, it is characterized in that: described native graphite is that fixed carbon content 〉=99.0%, particle diameter D50 are 8 ~ 25 microns class spherical natural graphite, the quality of described boracic hard carbon layer is 1 ~ 10% of a native graphite quality, and the quality of described soft carbon-coating is 1 ~ 10% of a native graphite quality.
3. the preparation method of lithium ion battery modified natural graphite negative material as claimed in claim 1 or 2 is characterized in that its step is as follows:
(1) the hard carbon presoma is dissolved in the organic solvent, the mass ratio of hard carbon presoma and organic solvent is 1:10 ~ 100, dissolves the back fully and adds boron-containing solution, and the back that stirs adds native graphite, abundant mixing, and decompression steams solvent and water;
(2) mixture in the step (1) is warmed up to 600 ~ 1000 ℃ with 2 ~ 3 ℃/minute speed, is incubated 1 ~ 5 hour, reduce to room temperature with 2 ~ 3 ℃/minute speed again, afterwards material fragmentation is sieved, the order number of sieve is 150 ~ 300 orders;
(3) with screenings in the step (2) and the abundant mixing of soft carbon precursor; under the environment of nitrogen or argon gas atmosphere protection; speed with 2 ~ 3 ℃/minute; be warmed up to 2500 ~ 3000 ℃ and carry out graphitization; be incubated 1 ~ 5 hour, reduce to room temperature with 2 ~ 3 ℃/minute speed again, the material fragmentation after the graphitization processing is sieved; the order number of sieve is 150 ~ 300, makes lithium ion battery modified natural graphite negative material.
4. the preparation method of lithium ion battery modified natural graphite negative material according to claim 3, it is characterized in that: the hard carbon precursor in the described step (1) is at least a in phenolic resins, epoxy resin, furane resins, poly furfuryl alcohol resin, polyacrylonitrile, Kynoar, the polyphenyl phenol, and carbon content is 50% ~ 70%.
5. the preparation method of lithium ion battery modified natural graphite negative material according to claim 3 is characterized in that: the organic solvent in the described step (1) is ethanol, acetone, benzene, toluene, benzinum, carbon disulfide or quinoline.
6. the preparation method of lithium ion battery modified natural graphite negative material according to claim 3, it is characterized in that: the boron-containing solution in the described step (1) is the ethanolic solution or the aqueous solution of boric acid, boron oxide, the mass concentration 1 ~ 5% of solution, the quality of boron element accounts for 0.1 ~ 8% of hard carbon layer quality.
7. the preparation method of lithium ion battery modified natural graphite negative material according to claim 3 is characterized in that: the equipment that adopts in the described step (2) is atmosphere box type furnace, push pedal tunnel kiln, tube furnace or kiln.
8. the preparation method of lithium ion battery modified natural graphite negative material according to claim 3 is characterized in that: the equipment that adopts in the described step (3) is acheson furnace, carbon shirt-circuiting furnace or tandem graphitizing furnace.
9. the preparation method of lithium ion battery modified natural graphite negative material according to claim 3 is characterized in that: the soft carbon precursor in the described step (3) is the mixture of petroleum asphalt or coal tar pitch or petroleum asphalt and coal tar pitch.
10. the preparation method of lithium ion battery modified natural graphite negative material according to claim 9 is characterized in that: the softening point of described petroleum asphalt or coal tar pitch is 200 ~ 290 ℃, and carbon content is 70 ~ 80%, and average grain diameter is 2 ~ 4 microns.
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Cited By (24)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102881869A (en) * | 2012-09-26 | 2013-01-16 | 东莞市翔丰华电池材料有限公司 | Modified hard carbon negative electrode material for lithium ion battery and preparation method for modified hard carbon negative electrode material |
| CN103078090A (en) * | 2013-03-01 | 2013-05-01 | 湖州创亚动力电池材料有限公司 | Lithium ion power battery composite cathode material and its preparation method |
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| CN102881869A (en) * | 2012-09-26 | 2013-01-16 | 东莞市翔丰华电池材料有限公司 | Modified hard carbon negative electrode material for lithium ion battery and preparation method for modified hard carbon negative electrode material |
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