CN101209831A - Carbon modified material for lithium ion secondary battery negative pole and preparation thereof - Google Patents
Carbon modified material for lithium ion secondary battery negative pole and preparation thereof Download PDFInfo
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- CN101209831A CN101209831A CNA2007103017235A CN200710301723A CN101209831A CN 101209831 A CN101209831 A CN 101209831A CN A2007103017235 A CNA2007103017235 A CN A2007103017235A CN 200710301723 A CN200710301723 A CN 200710301723A CN 101209831 A CN101209831 A CN 101209831A
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 23
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- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 2
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Classifications
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a carbon modified material applied in cathode of lithium-ion secondary batteries. The carbon modified material takes one or more of glucose, fructose, cane sugar, cellulose and starch as raw material, which is dissolved in organic solvent and treated by liquid phase dehydration processing in a pressure container, then is subject to surface coating modification, low temperature curing, carbonization and finally is heat treated at high temperature, cooled and sieved; the coating modification technique adopted by the invention overcomes defect of the prior thermolysis hard carbon material, and compared with common carbon material, the invention improves specific volumetric capacity and initial efficiency and reduces specific surface area, thus eliminating loss of reversible capacity due to sensitivity of thermolysis hard carbon material to air and improving processing property of material.
Description
Technical field
The present invention relates to a kind of raw material of wood-charcoal material and preparation method thereof, particularly lithium ion secondary battery cathode is material modified and its production and use with carbon microspheres.
Background technology
At present, along with being extensive use of and high speed development of various portable electric appts and power tool, requirement to chemical power source also improves in succession, lithium ion battery is the present more successful a kind of portable chemical power supply of exploitation, and it has, and voltage height, specific energy are big, discharging voltage balance, low-temperature performance is good, safety performance is excellent and easily store and advantage such as long working life.Yet current electronics miniaturization and microminiaturized degree are more and more higher, and be also more deep with application to the research of lithium ion battery.
At present, negative material adopts graphite material mostly in the commercial lithium ion battery, its advantage be have higher specific storage (＜372mAh/g), low electropotential (＜1.0Vvs.Li
+/ Li), high efficient first, long cycle life.Graphite material again because of its kind, preparation method and thermal treatment temp not simultaneously, can cause the difference on the The Nomenclature Composition and Structure of Complexes, and then cause the difference of embedding behavior and performance.
Graphite is divided into synthetic graphite and natural graphite again, and that synthetic graphite has is good with the electrolytic solution consistency, its embedding, to take off speed bigger, and load character etc. is preferably arranged.It promptly is the steady phase spherical carbon of Jie that raw material is made with pitch that PANASONIC has adopted graphited asphalt carbon microballoon, is called for short MCMB.But the volume and capacity ratio that it is low and first efficient be still waiting to improve.Natural graphite is current comparatively ideal negative material, has that cost is low, capacity is higher and characteristics such as compaction capacity is good, has just adopted natural graphite as SANYO GS company.Shortcoming is that they are relatively more responsive to some electrolytic solution, is subjected to the restriction of theoretical lithium storage content again, is difficult to increase substantially very much by improving battery preparation technique merely.
Therefore, have the novel negative material of higher capacity and Development of New Generation, become the hot subject in the Study on Li-ion batteries using field.Once, alloy material once had been the first-selection that people study, but efficient first that it is low and high volume effect cause relatively poor cyclical stability to fail to be well solved always, tin-oxide reversible capacity as the preparation of employing CVD methods such as Hironorid reaches 600mAh/g, but its irreversible capacity reaches 800mAh/g[J.PowerSources, 2001,97-98:229 especially], efficient is obviously on the low side first, its drawbacks limit its application in lithium ion battery.The compound system of the silicon grain external parcel amorphous carbon layer of the subordinate's of Hitachi MAXwell company preparation, though improved the structure and the conductivity of silicon materials, because its technological process is restive, uncertain factor is many, causes being difficult to realize producing in batches.Reported negative material among the Chinese invention patent CN01807830.3 by the hard charcoal preparation of pyrolysis, because of modifying on its surface, irreversible capacity is quite high, cause the high reason of irreversible capacity except electrode solution is decomposed to form passive film, the various active groups such as the hydroxyl of material surface, with and the moisture of absorption also be the major cause that forms irreversible capacity, though hydroxyl and moisture have been eliminated when pyrolysis; Because in the assembling and use of battery, if electrode and various reactive gass contact, as CO
2, O
2, also can strengthen irreversible reaction and lose reversible capacity, this also is the reason of commercialization pyrolyzed carbon materials to air-sensitive.
Summary of the invention
Thereby technical problem solved by the invention provide a kind of improved volume and capacity ratio and first efficient, reduced specific surface area and eliminated pyrolytic hard carbon material and air-sensitive lost the defective of reversible capacity, also improved carbon cathode material and its preparation method that the lithium-ion secondary cell of Drawing abillity is suitable for simultaneously.
The carbon modified material that a kind of lithium ion secondary battery negative pole uses, it is to be raw material with in glucose, fructose, sucrose, Mierocrystalline cellulose, the starch one or more, in pressurized vessel, carry out the liquid-phase dehydration processing again after being dissolved in organic solvent, then by coating modification, low-temperature curing, charing, after make after the high-temperature heat treatment, cooling screening; Its carbon modified material of making is sphere or elliposoidal, and median size is D50=0.5～30um, and tap density is between 0.5～1.5g/cc, and the BET specific surface area is at 0.5～5.0m
2Between/the g, real density 0.8～2.25g/cc, there are a large amount of nanoporouss its inside, aperture 0.1～0.6nm; Being used for the material of coating modification in the described carbon modified material accounts for the 5wt%～20wt% of total carbon modified material.
The carbon modified material that lithium ion secondary battery negative pole of the present invention uses, wherein said coating modification material is high softening-point coal-tar pitch, petroleum pitch or resin, and the softening temperature of pitch class material is 150～280 ℃, and meso-position radius is below 4um.
The carbon modified material that lithium ion secondary battery negative pole of the present invention uses, wherein said resin is furane resin, urea-formaldehyde resin, resol, Resins, epoxy, polymethylmethacrylate, polyvinylidene difluoride (PVDF) or polyacrylonitrile.
The preparation method of the carbon modified material that lithium ion secondary battery negative pole of the present invention uses, the step of preparation process of employing is as follows:
(1) presoma preparation:
One or more and organic solvent in glucose, fructose, sucrose, Mierocrystalline cellulose, the starch are formed mixture, add a certain amount of styrene-butadiene rubber(SBR) and a spot of span80 activator therein, form the homodisperse system of any concentration; Then the homodisperse system is placed the pressurized vessel of belt stirrer, heating is stirred simultaneously, and heat-up rate is 10～50 ℃/min, and temperature is controlled at 200～380 ℃, and soaking time is 5～20 hours; Cooling is broken up then, crosses 200～500 mesh sieves and gets presoma;
(2) modification is handled:
Is that 10: 0.08～2.0 ratios are mixed with the presoma for preparing by weight with the coating modification material, heating then, and temperature is controlled at 150～280 ℃, mixes;
(3) thermal treatment:
The powder that taking-up mixes is packed into and is heated in corundum crucible or the plumbago crucible, and Heating temperature is 400～1300 ℃, and be 5～40 hours heat-up time; Powder after will heating again carries out high-temperature roasting, and maturing temperature is more than 2400 ℃, and roasting time is 2～48 hours;
(4) screening packing:
Powder after the roasting is carried out selected screening, and sieve number is 100～500 orders, at last by specifying the requirement packing.
The preparation method of the carbon modified material that lithium ion secondary battery negative pole of the present invention uses, wherein said organic solvent is benzene, toluene, ethylbenzene, dimethylbenzene, cycloalkanes, sherwood oil, quinoline, thiophene or dithiocarbonic anhydride.
The preparation method of carbon modified material of the present invention, also be included in the particle diameter of controlling bead by the cohesion and the residence time of adjusting homogeneous mixture system under the High Temperature High Pressure, pressure is greater than 15atm, and residence time was controlled at 5～48 hours, makes microspherulite diameter be tending towards constant.
The preparation method of carbon modified material of the present invention, also being included on the presoma described in the step (1) has a large amount of nanometer micropores, and the size of micropore is approximately 0.1～0.6nm.
The preparation method of carbon modified material of the present invention, feed shielding gas in the step (3) during thermal treatment, described shielding gas is nitrogen, rare gas element or its mixed gas, gas flow rate is 10～20L/min, during thermal treatment, below 600 ℃ the time, heat-up rate is controlled to be 50～100 ℃/hour; More than 600 ℃ the time, heat-up rate is controlled to be 200～300 ℃/hour.
The preparation method of carbon modified material of the present invention, when used coating modification material normal temperature was down solid-state in the step (2), its meso-position radius should be less than 3um, and the ratio that accounts for total carbon modified material is not more than 18wt%.
Carbon modified material of the present invention is widely used in the ion secondary battery cathode material lithium.
The present invention adopts the coating modification technology to overcome the shortcoming of existing pyrolytic hard carbon material, compare with common raw material of wood-charcoal material, volume and capacity ratio and efficient have first been improved, reduced specific surface area, so not only eliminate pyrolytic hard carbon material air-sensitive has been lost reversible capacity, also improved Drawing abillity.The characteristics of maximum of the present invention are that its preparation technology's flow process is simple simultaneously, process is easy to control, cost of manufacture is low, environmentally friendly etc., this material can not only satisfy the demand of high magnification capacity, can stop to overcharge and cross to put, reversible capacity and first efficient all be significantly improved, in lithium ion battery applications, open up new way, be fit to commercial exploitation.
Description of drawings
Fig. 1 is that carbon modified material in the embodiment of the invention one is as the first charge-discharge curve of lithium ion battery negative material;
Fig. 2 is that carbon modified material in the embodiment of the invention two is as the first charge-discharge curve of lithium ion battery negative material;
Fig. 3 is that carbon modified material in the embodiment of the invention six is as the first charge-discharge curve of lithium ion battery negative material.
Embodiment
The present invention is further illustrated below by embodiment.
Embodiment one:
Take by weighing 150 gram glucose and pour in 500 milliliters the clean beaker, add solvent dithiocarbonic anhydride 300 grams then, fully stirred 2 hours under stirrer, rotating speed is adjusted to 1000 rev/mins, it is fully dissolved form the homodisperse system; Adding the styrene-butadiene rubber(SBR) of 20 grams 50% and the span80 of 3 grams 3% in the homodisperse system activates, continue to stir 1 hour, be placed on afterwards in the pressurized vessel of 1 liter of belt stirrer, the limit heating starts simultaneously stirs, stirring velocity is 500 rev/mins, speed with 10 ℃/min is warmed up to 350 ℃, is incubated to take out after 12 hours to be cooled to normal temperature, breaks up 325 mesh sieves and obtains presoma.
The petroleum pitch of getting 100 gram presomas and 10 gram softening temperatures then and be 200 ℃, meso-position radius and be 3um mixes, even back to be mixed take out the plumbago crucible of packing into carry out in warm processing, thermal treatment temp is 1100 ℃, treatment time is 8 hours, feed nitrogen in the heat treatment process and protect, also can feed other rare gas element such as argon gas or its mixed gas; Powder after afterwards middle temperature being handled carries out pyroprocessing at 2800 ℃, feeds shielding gas simultaneously, and the treatment time is 20 hours.At last powder is cooled to cross 200 mesh sieves behind the normal temperature, the powder behind the sieve is modification powdered carbon sample.
Take by weighing active substance modification powdered carbon and binding agent polyvinylidene difluoride (PVDF) in 94: 6 ratio (mass ratio) again, it is dissolved in dimethyl pyrrolidone, stir repeatedly, be coated in active substance on the copper mesh equably again after binding agent and powdered carbon are mixed, vacuum-drying 12h, last compressing tablet, weighing require the electrode slice quality at 10～15mg.Electrochemical property test adopts the Experimental cell of two electrode structures, and negative material is a carbon modified material, lithium sheet just very, and the copper pool is collector; Electrolytic solution is 1mol/LLiClO
4The solution of/NSC 11801 (EC)+diethyl carbonate (DEC); Barrier film is Celgard2400.Battery assembles in relative humidity is lower than 5% dry glove box and finishes.When requirement discharged and recharged, still in loft drier, test current density was 0.1mA/cm to battery model
2, the charging stopping potential is 2.00V, discharge cut-off voltage is 0.001V.
The loading capacity first of this material is 392.8mAh/g, and first charge-discharge efficiency is 95.4%.
Embodiment two:
Take by weighing 120 gram fructose and be contained in 500 milliliters the clean beaker, add solvent dithiocarbonic anhydride 250 grams then, be made into the homodisperse system; The span80 of the styrene-butadiene rubber(SBR) of adding 30 grams 50% and 5 grams 3% activates and obtains presoma in the homodisperse system.
Get 100 gram presomas again and 12 gram softening temperatures are 220 ℃ coal-tar pitch mixing coating modification.
Present embodiment other parts and embodiment one are identical.
The loading capacity first of this material is 384.7mAh/g, and first charge-discharge efficiency is 93.9%.
Embodiment three:
Take by weighing 100 gram glucose and 80 gram fructose are contained in 500 milliliters the clean beaker, add solvent xylene 320 grams then, fully stirred 2 hours under stirrer, rotating speed is adjusted to 1200 rev/mins, it is fully dissolved form the homodisperse system; The span80 of the styrene-butadiene rubber(SBR) of adding 35 grams 50% and 4 grams 3% activates and obtains presoma in the homodisperse system.
Get 100 gram presomas again and 15 gram softening temperatures are that 240 ℃, meso-position radius are the coal-tar pitch mixing coating modification of 3um.In the warm treatment time be 12 hours, carried out pyroprocessing 24 hours at 2800 ℃ again.
Present embodiment other parts and embodiment one are identical.
Detection learns that the loading capacity first of this material is 398.9mAh/g, and first charge-discharge efficiency is 94.5%.
Embodiment four:
Take by weighing 130 gram glucose and 50 gram starch are contained in 500 milliliters the clean beaker, add solvent dithiocarbonic anhydride 200 grams and dimethylbenzene 140 grams then, fully stirred 3 hours under stirrer, rotating speed is adjusted to 1200 rev/mins, it is fully dissolved form the homodisperse system; The span80 of the styrene-butadiene rubber(SBR) of adding 15 grams 50% and 5 grams 3% activates and obtains presoma in the homodisperse system.
Coal-tar pitch and the 7 gram softening temperatures of getting 100 gram presomas and 8 gram softening temperatures again and be 240 ℃ are 220 ℃ petroleum pitch mixing coating modification.In warm treatment temp be 1200 ℃, heat treatment time is 20 hours, carries out high-temperature heat treatment 36 hours at 3000 ℃ again.
Present embodiment other parts and embodiment one are identical.
The loading capacity first of this material is 385.7mAh/g, and first charge-discharge efficiency is 92.8%
Embodiment five:
Take by weighing 110 gram glucose and be contained in 500 milliliters the clean beaker, add solvent dithiocarbonic anhydride 230 grams and quinoline 120 grams then, fully stirred 1 hour under stirrer, rotating speed is adjusted to 1300 rev/mins, makes it fully dissolve formation homodisperse system; The span80 of the styrene-butadiene rubber(SBR) of adding 18 grams 50% and 6 grams 3% activates and obtains presoma in the homodisperse system.
Get 100 gram presomas again and 8 gram softening temperatures are that 230 ℃, meso-position radius are the coal-tar pitch mixing coating modification of 2um.
Present embodiment other parts and embodiment one are identical.
The loading capacity first of this material is 395.5mAh/g, and first charge-discharge efficiency is 93.6%
Embodiment six:
Take by weighing 80 gram fructose and 100 gram starch are contained in 500 milliliters the clean beaker, add then in solvent dithiocarbonic anhydride 350 grams, fully stirred 5 hours under stirrer, rotating speed is adjusted to 800 rev/mins, it is fully dissolved form the homodisperse system; The span80 of the styrene-butadiene rubber(SBR) of adding 19 grams 50% and 4 grams 3% activates and obtains presoma in the homodisperse system.
Get 100 gram presomas again and 12 gram softening temperatures are 240 ℃ coal-tar pitch mixing coating modification.In warm treatment temp be 1000 ℃, heat treatment time is 8 hours, carries out high-temperature heat treatment 12 hours at 2900 ℃ again.
Present embodiment other parts and embodiment one are identical.
The loading capacity first of this material is 376.1mAh/g, and first charge-discharge efficiency is 93.2%
Embodiment seven:
Taking by weighing glucose, fructose and starch respectively 50 restrains in the clean beaker that is contained in 500 milliliters, add solvent dithiocarbonic anhydride 150 grams and sherwood oil 200 grams then, fully stirred 6 hours under stirrer, rotating speed is adjusted to 1500 rev/mins, it is fully dissolved form the homodisperse system; The span80 of the styrene-butadiene rubber(SBR) of adding 35 grams 50% and 6 grams 3% activates and obtains presoma in the homodisperse system.
Get 100 gram presomas again and 12 gram softening temperatures are 240 ℃ coal-tar pitch mixing coating modification.In warm treatment temp be 1200 ℃, heat treatment time is 16 hours, carries out high-temperature heat treatment 24 hours at 3000 ℃ again.
Present embodiment other parts and embodiment one are identical.
The loading capacity first of this material is 389.9mAh/g, and first charge-discharge efficiency is 95.0%
Embodiment eight:
Take by weighing 130 gram glucose and 50 gram starch are contained in 500 milliliters the clean beaker, add solvent dithiocarbonic anhydride 380 grams then, fully stirred 5 hours under stirrer, rotating speed is adjusted to 1500 rev/mins, it is fully dissolved form the homodisperse system; The span80 of the styrene-butadiene rubber(SBR) of adding 50 grams 50% and 8 grams 3% activates and obtains presoma in the homodisperse system.
Get 100 gram presomas again and 11 gram softening temperatures are 240 ℃ coal-tar pitch mixing coating modification.In warm treatment temp be 1200 ℃, heat treatment time is 18 hours, carries out high-temperature heat treatment 24 hours at 3000 ℃ again.
Present embodiment other parts and embodiment one are identical.
The loading capacity first of this material is 402.5mAh/g, and first charge-discharge efficiency is 91.3%
Subordinate list is the electrical performance data of carbon modified material in the various embodiments of the present invention.
Claims (10)
1. the carbon modified material that uses of a lithium ion secondary battery negative pole, it is characterized in that: it is to be raw material with in glucose, fructose, sucrose, Mierocrystalline cellulose, the starch one or more, in pressurized vessel, carry out the liquid-phase dehydration processing again after being dissolved in organic solvent, then by coating modification, low-temperature curing, charing, after make after the high-temperature heat treatment, cooling screening; Its carbon modified material of making is sphere or elliposoidal, and median size is D50=0.5～30um, and tap density is between 0.5～1.5g/cc, and the BET specific surface area is at 0.5～5.0m
2Between/the g, real density 0.8～2.25g/cc, there are a large amount of nanoporouss its inside, aperture 0.1～0.6nm; Being used for the material of coating modification in the described carbon modified material accounts for the 5wt%～20wt% of total carbon modified material.
2. the carbon modified material that lithium ion secondary battery negative pole according to claim 1 uses, it is characterized in that: wherein said coating modification material is high softening-point coal-tar pitch, petroleum pitch or resin, the softening temperature of pitch class material is 150～280 ℃, and meso-position radius is below 4um.
3. the carbon modified material that lithium ion secondary battery negative pole according to claim 2 uses, it is characterized in that: wherein said resin is furane resin, urea-formaldehyde resin, resol, Resins, epoxy, polymethylmethacrylate, polyvinylidene difluoride (PVDF) or polyacrylonitrile.
4. the preparation method of the carbon modified material that uses of a lithium ion secondary battery negative pole, it is characterized in that: the step of preparation process of employing is as follows:
(1) presoma preparation:
One or more and organic solvent in glucose, fructose, sucrose, Mierocrystalline cellulose, the starch are formed mixture, add a certain amount of styrene-butadiene rubber(SBR) and a spot of span80 activator therein, form the homodisperse system of any concentration; Then the homodisperse system is placed the pressurized vessel of belt stirrer, heating is stirred simultaneously, and heat-up rate is 10～50 ℃/min, and temperature is controlled at 200～380 ℃, and soaking time is 5～20 hours; Cooling is broken up then, crosses 200～500 mesh sieves and gets presoma;
(2) modification is handled:
Is that 10: 0.08～2.0 ratios are mixed with the presoma for preparing by weight with the coating modification material, heating then, and temperature is controlled at 150～280 ℃, mixes;
(3) thermal treatment:
The powder that taking-up mixes is packed into and is heated in corundum crucible or the plumbago crucible, and Heating temperature is 400～1300 ℃, and be 5～40 hours heat-up time; Powder after will heating again carries out high-temperature roasting, and maturing temperature is more than 2400 ℃, and roasting time is 2～48 hours;
(4) screening packing:
Powder after the roasting is carried out selected screening, and sieve number is 100～500 orders, at last by specifying the requirement packing.
5. the preparation method of the carbon modified material that lithium ion secondary battery negative pole according to claim 4 uses, wherein said organic solvent is benzene, toluene, ethylbenzene, dimethylbenzene, cycloalkanes, sherwood oil, quinoline, thiophene or dithiocarbonic anhydride.
6. the preparation method of carbon modified material according to claim 4, it is characterized in that: also be included in the particle diameter of controlling bead by the cohesion and the residence time of adjusting homogeneous mixture system under the High Temperature High Pressure, pressure is greater than 15atm, residence time was controlled at 5～48 hours, made microspherulite diameter be tending towards constant.
7. the preparation method of carbon modified material according to claim 4, it is characterized in that: also being included on the presoma described in the step (1) has a large amount of nanometer micropores, and the size of micropore is approximately 0.1～0.6nm.
8. the preparation method of carbon modified material according to claim 4, it is characterized in that: feed shielding gas in the step (3) during thermal treatment, described shielding gas is nitrogen, rare gas element or its mixed gas, gas flow rate is 10～20L/min, during thermal treatment, below 600 ℃ the time, heat-up rate is controlled to be 50～100 ℃/hour; More than 600 ℃ the time, heat-up rate is controlled to be 200～300 ℃/hour.
9. the preparation method of carbon modified material according to claim 4 is characterized in that: when solid-state, its meso-position radius should be less than 3um down for used coating modification material normal temperature in the step (2), and the ratio that accounts for total carbon modified material is not more than 18wt%.
10. any application of described carbon modified material in ion secondary battery cathode material lithium among the claim 1-3.
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