CN1318872A - Lithium ion battery negative pole material and its preparation and use - Google Patents
Lithium ion battery negative pole material and its preparation and use Download PDFInfo
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- CN1318872A CN1318872A CN00105640A CN00105640A CN1318872A CN 1318872 A CN1318872 A CN 1318872A CN 00105640 A CN00105640 A CN 00105640A CN 00105640 A CN00105640 A CN 00105640A CN 1318872 A CN1318872 A CN 1318872A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The negative pole material is material with core-shell structure, the core is natural graphite with nanometer level pores or cracks on the surface, the shell is high molecular pyrolysis carbon, and the shell-to-core weight ratio is 0.05-0.8. It is prepared by the processes of chemical treatment, modification with high molecular electrolyte, resin coating and final sintering at 800 deg.c. The present inventino has the following effects: raised adhesion of the negative pole material to plate without peeling off after 100 times of charge and discharge circulation; raised lithium ion battery capacity by 10-30 %; and raised circulation life of lithium ion battery by 10-20%.
Description
The present invention relates to a kind of lithium ion battery negative material, particularly relate to a kind of carbon negative pole material that is used for lithium ion battery and preparation method thereof.
Lithium ion battery has advantages such as capacity is big, average output voltage is high, non-environmental-pollution, can make the power supply of mobile electronic products such as mobile phone, notebook computer, field camera, can also be as the power supply of electronic products such as camera, calculator, wrist-watch.
For further improving the performance of lithium ion battery, people have carried out deep research to carbon negative pole material.With native graphite after physics or chemical method are handled, as carbon negative electrode material of lithium ion cell, exist bad adhesion with pole plate, carbon negative pole material is easy to come off from pole plate in the cycle charge discharge electric process, influenced cycle life [J.Electrochem.Soc., 144 (4) 1195 (1997) J.Electrochem.Soc., 146 (11) 3963 (1999) Journal of PowerSources, 68 187 (1997) Journal ofPower Sources 68 291 (1997)] cycle life when especially having reduced high current charge-discharge; With pitch, petroleum coke, coal tar is the Delanium that raw material is made through high-temperature heat treatment, as carbon negative electrode material of lithium ion cell, it exists the not high shortcoming of electrochemistry capacitance [spy open flat 4-115458, spy open flat 5-307958, spy open flat 5-234584, the spy opens flat 9-259886]; As lithium ion battery negative material, it exists, and open circuit voltage is low, the shortcoming of cycle life difference [spy opens flat 3-245458, the spy opens flat 9-259883, U.S.Patent 4601849] with macromolecule cracking carbon; And above-mentioned carbon negative pole material obtained new negative material after compound, modification, and still, cycle life still undesirable [spy opens flat 5-74452].
The objective of the invention is to overcome existing carbon negative electrode material of lithium ion cell, the shortcoming of low with pole plate bad adhesion, electrochemistry capacitance in the plate forming process, cycle life difference, and provide a kind of is raw material with the native graphite, and skin is coated with the carbon negative pole material with shell-core structure of macromolecule cracking carbon.Use lithium ion battery negative material of the present invention can improve carbon negative electrode material of lithium ion cell in the plate forming process with the caking property of pole plate and improve the electrochemistry capacitance of lithium ion battery and the life-span of cycle charge-discharge.
Lithium ion battery negative material of the present invention is the carbon negative pole material with shell-core structure.Shell is a kind of macromolecule cracking carbon with undefined structure, and it is the macromolecule cracking carbon matrix precursor that monomer is prepared after the crosslinking agent polymerization, obtains behind high temperature pyrolysis; Nuclear is high-crystallinity, and aspect has the native graphite in nanoscale hole or crack.The presoma of cracking carbon be 0.1～1.0: 1 by the weight part ratio of coated natural graphite.Lithium ion battery negative material preparation method of the present invention is as follows:
1. the liquid phase chemical of native graphite is handled: it is in 30～50% the inorganic acid aqueous solution that native graphite is joined concentration, then, handled 2-200 hour down at 20-120 ℃, filter, be washed to neutrality, oven dry, the acquisition aspect has the native graphite in nanoscale hole or crack.
2. the modification of polymer solid electrolyte: the native graphite of above-mentioned processing is evenly mixed with polymer solid electrolyte, obtaining finishing has the native graphite of polymer solid electrolyte, and the weight part ratio of native graphite and polymer solid electrolyte is 1: 0.05～0.3.
3. the coating of macromolecule presoma: the above-mentioned native graphite that is modified with solid electrolyte is carried out polymerization reaction with monomer, crosslinking agent, obtain the native graphite that the surface is coated with the macromolecule presoma, the ratio of macromolecule presoma and native graphite is 0.1～1.0: 1, and wherein the weight part ratio of monomer and crosslinking agent is 1: 0.01-0.4.
4. sintering process: with the above-mentioned native graphite that is coated with the macromolecule presoma; put into the sintering furnace of inert gas shielding; at 500-1000 ℃ of following sintering 1-48 hour; obtain the shell-core structure lithium ion battery negative material that has of the present invention, the weight part ratio of its mesochite-nuclear is 0.05-0.8: 1.
Negative material and anode material for lithium-ion batteries, barrier film, electrolyte or the solid electrolyte of method for preparing are assembled into lithium ion battery or solid lithium ion battery.
Carbon negative electrode material of lithium ion cell of the present invention is under ESEM, and the nuclear that can be observed carbon negative pole material partly has significantly, is different from the staged layer structure of native graphite; The cracking carbon structure that partly presents smooth sphere or curved surface at its shell, this is because native graphite is passivated through polymer solid electrolyte modification rear surface, polymer solid electrolyte is filled in the both sides of the sharp-pointed faceted pebble of native graphite, make the surface of native graphite have preliminary curved surface structure, in next step high molecular polymerization process, the macromolecule presoma is deposited on the curved surface uniformly, the surface that has obtained to be spherical is coated with the native graphite of macromolecule presoma, presents uniform shell-core structure behind the sintering.This structure helps improving the caking property of carbon negative pole material and pole plate, helps improving the capacity and the cycle life of lithium ion battery.
The lithium ion battery that adopts this patent invention to make has overcome the shortcoming of lithium ion battery in the past, obtained following invention effect: (1) has improved the caking property of carbon negative pole material and pole plate, and carbon negative pole material does not have obscission from pole plate behind 100 cycle charge-discharges; (2) capacity of lithium ion battery has improved 10%～30%; (3) cycle life of lithium ion battery has improved 10-20%.
By the following examples detailed process of the present invention is described further.[embodiment 1]
1. the 100g native graphite is joined 300g concentration and be in 50% the sulfuric acid solution, 80 ℃ of reactions 6 hours down, filter, be washed to neutrality, oven dry then, the acquisition aspect has the graphite of nanometer micropore.
2. the graphite that will handle and 35g molecular weight are that 5000 polyethylene glycol oxide and 150g water evenly mix, add 30g acrylonitrile, 3g divinylbenzene and initator then, reacted 6 hours down at 85 ℃, filter, dry, obtain being coated with the graphite of crosslinked polypropylene eyeball.
3. the graphite after will coating is put into the stove of argon shield, obtains negative material of the present invention in 8 hours at 600 ℃ of following sintering.
Lithium ion battery negative material and anode material for lithium-ion batteries LiCoO with method for preparing
2With the vinylidene is the pole plate binding agent, make the negative plate and the positive plate of lithium ion battery respectively, be electrode diaphragm with the microporous polypropylene membrane, be glycol dimethyl ether with the volume ratio: the 1M lithium hexafluoro phosphate of vinyl carbonate=1: 1 is that electrolyte or cross-linking type polyethylene glycol oxide sulfonic acid lithium are that solid electrolyte is assembled into lithium ion battery or solid lithium ion battery.[embodiment 2]
1. handle native graphite according to the method for embodiment 1.
2. the graphite that will handle evenly mixes with 20g polyacrylic acid and 150g water, adds 30g acrylonitrile, 6g divinylbenzene and initator then, reacts 6 hours down at 85 ℃, filters, dries, and obtains to be coated with the graphite of crosslinked polypropylene eyeball.
3. the graphite after will coating is put into the stove of argon shield, obtains negative material of the present invention in 6 hours at 800 ℃ of following sintering.[embodiment 3]
1. the 100g native graphite is joined in the perchloric acid solution of 300g 30%, reacted 12 hours down at 70 ℃, filter, be washed to neutrality, oven dry then, the acquisition aspect has the graphite of nanometer micropore.
2. the graphite that will handle evenly mixes with 40g polymethylacrylic acid and 150g water, adds 30g styrene, 3g divinylbenzene and initator then, reacts 6 hours down at 85 ℃, filters, dries, and obtains to be coated with the graphite of crosslinked polystyrene.
3. the graphite after will coating is put into the stove of argon shield, obtains negative material of the present invention in 8 hours at 700 ℃ of following sintering.[embodiment 4]
1. the 100g native graphite is joined in the salpeter solution of 300g 40%, reacted 5 hours down at 40 ℃, filter, be washed to neutrality, oven dry then, the acquisition aspect has the graphite of nanometer micropore.
2. the graphite that will handle evenly mixes with 25g polymethyl methacrylate and 100g toluene, and toluene is removed in oven dry then, obtains the graphite that polymethyl methacrylate is modified.The graphite of 12.5g bisphenol-A, 23.5g epoxychloropropane and polymethyl methacrylate modified is evenly mixed, and be heated to 50 ℃, in 30 minutes, drip the NaOH solution of 12.5ml 20%, be warming up to 95 ℃ of reactions 1 hour, obtain being coated with the graphite of epoxy resin after vacuum distillation removes and anhydrates.
3. the graphite after will coating is put into the stove of argon shield, obtains negative material of the present invention in 8 hours at 800 ℃ of following sintering.[embodiment 5]
1. the 100g native graphite is joined in the periodic acid solution of 300g 20%, reacted 12 hours down at 70 ℃, filter, be washed to neutrality, oven dry then, the acquisition aspect has the graphite of nanometer micropore.
2. the graphite that will handle evenly mixes with 30g polyacrylonitrile and 100gN-methyl pyrrolidone, and then, the N-methyl pyrrolidone is removed in oven dry then, obtains the graphite that polyacrylonitrile is modified.35.29g phenol, 62.5g formalin (content＞36%) are evenly mixed with the graphite of polyacrylonitrile modified and the NaOH aqueous solution of 2.22g 20%, be heated with stirring to 75 ℃ of reactions 1 hour, be warming up to again under the counterflow condition and reacted 1 hour, obtain to be coated with the graphite of phenolic resins after vacuum distillation dewaters.
3. the graphite after will coating is put into the stove of argon shield, obtains negative material of the present invention in 6 hours at 800 ℃ of following sintering.[embodiment 6]
1. handle native graphite according to the method for embodiment 1.
2. the graphite that will handle and 20g molecular weight are that 10000 polyethylene glycol oxide and 150g water evenly mix, then, add and 200g toluene, 30g styrene, 5g divinylbenzene and initator, reacted 6 hours down at 85 ℃, filter, dry, obtain to be coated with the graphite of crosslinked polystyrene.
1. the graphite after will coating is put into the stove of argon shield, obtains negative material of the present invention [comparative example 1] in 8 hours at 700 ℃ of following sintering
1. the native graphite 100g that will handle without chemical liquid phase and 20g molecular weight are that 2000 polyethylene glycol oxide and 150g water evenly mix, add 30g styrene, 3g divinylbenzene and initator then, reacted 6 hours down at 85 ℃, filter, dry, obtain to coat the graphite of crosslinked polystyrene.
2. the graphite after will coating is put into the stove of argon shield, obtains negative material of the present invention in 8 hours at 700 ℃ of following sintering.[comparative example 2]
1. 150g water is evenly mixed with 30g styrene, 3g divinylbenzene and initator, then, reacted 6 hours down, filter, dry, obtain crosslinked polystyrene at 85 ℃.
2. crosslinked polystyrene is put into the stove of argon shield, obtained negative material of the present invention in 8 hours at 700 ℃ of following sintering.[comparative example 3]
Handle native graphite according to the method among the embodiment 1, directly as carbon negative electrode material of lithium ion cell.[comparative example 4]
1. handle native graphite according to the method for embodiment 1.
2. the graphite that will handle evenly mixes with 150g water, adds 30g acrylonitrile, 6g divinylbenzene and initator then, reacts 6 hours down at 85 ℃, filters, dries, and obtains to be coated with the graphite of crosslinked polypropylene eyeball.
3. the graphite after will coating is put into the stove of argon shield, obtains negative material of the present invention in 6 hours at 800 ℃ of following sintering.
Claims (9)
1. lithium ion battery negative material, it is characterized in that described negative material is is shell with unformed macromolecule cracking carbon, aspect has the carbon negative pole material of the native graphite in nanoscale hole or crack for nuclear, and the weight part ratio of its mesochite and nuclear is 0.05-0.8: 1.
2. according to claim 1, a kind of lithium ion battery cathode material and its preparation method is characterized in that carrying out in the following order:
(1) native graphite being joined concentration is in 30～50% the inorganic acid aqueous solution, then, handles 2-200 hour down at 20-120 ℃, filters, is washed to neutrality, oven dry, and the acquisition aspect has the native graphite in nanoscale hole or crack.
(2) native graphite with above-mentioned processing evenly mixes with polymer solid electrolyte, obtains the native graphite that finishing has polymer solid electrolyte, and the weight part ratio of native graphite and polymer solid electrolyte is 1: 0.05～0.3.
(3) the above-mentioned native graphite that is modified with polymer solid electrolyte is carried out polymerization reaction with monomer, crosslinking agent, obtain the native graphite that the surface is coated with the macromolecule presoma, the ratio of macromolecule presoma and native graphite is 0.1～1.0: 1, and wherein the weight part ratio of monomer and crosslinking agent is 1: 0.01-0.4.
(4) with the above-mentioned native graphite that is coated with the macromolecule presoma; put into the sintering furnace of inert gas shielding; at 500-1000 ℃ of following sintering 1-48 hour, obtain the shell-core structure lithium ion battery negative material that has of the present invention, the weight part ratio of its mesochite-nuclear is 0.05-0.8: 1.
3. according to claim 2, a kind of lithium ion battery cathode material and its preparation method is characterized in that described polymer solid electrolyte is: polyethylene glycol oxide, polyacrylic acid, poly-methylpropanoic acid, poly-methylpropanoic acid methyl esters, polyacrylonitrile.
4. according to claim 2, a kind of lithium ion battery cathode material and its preparation method is characterized in that described monomer is styrene, acrylonitrile.
5. according to claim 2, a kind of lithium ion battery cathode material and its preparation method, crosslinking agent is a divinylbenzene when it is characterized in that described monomer is styrene, acrylonitrile, the weight part ratio of monomer and crosslinking agent is 1: 0.01-0.4.
6. according to claim 2, a kind of lithium ion battery cathode material and its preparation method is characterized in that described macromolecule presoma is the styrene of cross-linking type polystyrene and cross-linking type polyacrylonitrile and cross-linking type and the copolymer of acrylonitrile.
7. according to claim 2, a kind of lithium ion battery cathode material and its preparation method is characterized in that described macromolecule presoma is cross-linking type phenolic resins, cross-linking type Lauxite, cross-linking type epoxy resin.
8. according to claim 1, a kind of lithium ion battery cathode material and its preparation method is characterized in that described carbon negative pole material is used to assemble the negative material of lithium ion battery.
9. according to claim 1, a kind of lithium ion battery cathode material and its preparation method is characterized in that described carbon negative pole material is used to assemble the negative material of solid lithium ion battery.
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| CN00105640A CN1318872A (en) | 2000-04-14 | 2000-04-14 | Lithium ion battery negative pole material and its preparation and use |
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| CN00105640A CN1318872A (en) | 2000-04-14 | 2000-04-14 | Lithium ion battery negative pole material and its preparation and use |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383996C (en) * | 2005-07-21 | 2008-04-23 | 复旦大学 | Carbon negative pole material with nano-hole and producing method and application thereof |
| CN101740230B (en) * | 2009-12-09 | 2011-11-23 | 中南大学 | Carbon compound cathode material for ultracapacitor battery |
| CN103482606A (en) * | 2013-09-23 | 2014-01-01 | 辽宁弘光科技(集团)有限公司 | Production method for intermediate phase carbon anode material |
| CN103199251B (en) * | 2013-03-05 | 2016-08-10 | 东莞新能源科技有限公司 | A kind of cathode material of lithium ion battery and preparation method thereof |
| CN106953076A (en) * | 2017-03-24 | 2017-07-14 | 中南大学 | A kind of sodium-ion battery carbon/carbon compound material and preparation method thereof |
| CN107507980A (en) * | 2016-06-14 | 2017-12-22 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of hard carbon composite cathode material of silicon/carbon/graphite |
| CN108598388A (en) * | 2018-03-23 | 2018-09-28 | 格林美（无锡）能源材料有限公司 | A kind of C/SiO2Coat lithium electricity tertiary cathode material and preparation method thereof |
| CN114335460A (en) * | 2021-12-21 | 2022-04-12 | 惠州市禾腾能源科技有限公司 | Quick-filling graphite composite material and preparation method thereof |
-
2000
- 2000-04-14 CN CN00105640A patent/CN1318872A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383996C (en) * | 2005-07-21 | 2008-04-23 | 复旦大学 | Carbon negative pole material with nano-hole and producing method and application thereof |
| CN101740230B (en) * | 2009-12-09 | 2011-11-23 | 中南大学 | Carbon compound cathode material for ultracapacitor battery |
| CN103199251B (en) * | 2013-03-05 | 2016-08-10 | 东莞新能源科技有限公司 | A kind of cathode material of lithium ion battery and preparation method thereof |
| CN103482606A (en) * | 2013-09-23 | 2014-01-01 | 辽宁弘光科技(集团)有限公司 | Production method for intermediate phase carbon anode material |
| CN103482606B (en) * | 2013-09-23 | 2015-06-17 | 大连宏光锂业股份有限公司 | Production method for intermediate phase carbon anode material |
| CN107507980A (en) * | 2016-06-14 | 2017-12-22 | 宁波杉杉新材料科技有限公司 | A kind of preparation method of hard carbon composite cathode material of silicon/carbon/graphite |
| CN106953076A (en) * | 2017-03-24 | 2017-07-14 | 中南大学 | A kind of sodium-ion battery carbon/carbon compound material and preparation method thereof |
| CN106953076B (en) * | 2017-03-24 | 2019-07-30 | 中南大学 | A kind of sodium-ion battery carbon/carbon compound material and preparation method thereof |
| CN108598388A (en) * | 2018-03-23 | 2018-09-28 | 格林美（无锡）能源材料有限公司 | A kind of C/SiO2Coat lithium electricity tertiary cathode material and preparation method thereof |
| CN114335460A (en) * | 2021-12-21 | 2022-04-12 | 惠州市禾腾能源科技有限公司 | Quick-filling graphite composite material and preparation method thereof |
| CN114335460B (en) * | 2021-12-21 | 2022-09-13 | 惠州市禾腾能源科技有限公司 | Quick-filling graphite composite material and preparation method thereof |
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