CN1061472C - Carbon material for cathode of lithium secondry battery - Google Patents
Carbon material for cathode of lithium secondry battery Download PDFInfo
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- CN1061472C CN1061472C CN96114133A CN96114133A CN1061472C CN 1061472 C CN1061472 C CN 1061472C CN 96114133 A CN96114133 A CN 96114133A CN 96114133 A CN96114133 A CN 96114133A CN 1061472 C CN1061472 C CN 1061472C
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- carbon
- negative pole
- secondary battery
- lithium secondary
- pole material
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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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The present invention relates to a carbon material for a cathode of a secondary lithium battery and a preparation method thereof. The carbon material comprises an amorphous carbon material, electric conduction carbon black and an adhesive, wherein the Is rail electron binding energy of the amorphous carbon material is composed of three parts of 288.4 to 287.4eV, 286.8 to 285.8eV and 285.4 to 284.0eV. in the preparation method for the carbon material for a cathode of a secondary lithium battery, carbon obtained by the method that a linear or cross-linked polymer is cracked and treated by heat is mixed with the electric conduction carbon black and the adhesive, and the carbon material can be obtained. The carbon material for cathode of a secondary lithium battery, which is obtained by the present invention, has lower cracking temperature as compared with conventional temperature and has reversible lithium storage capacity.
Description
The present invention relates to a kind ofly, specially refer to a kind of lithium secondary battery carbon negative pole material and preparation method thereof by the electrode that comprises active material.
The carbon negative pole material of the lithium secondary battery of research is many at present, Delanium, native graphite, chemical vapour deposition (CVD) charcoal, petroleum coke, acetylene black etc. (can referring to the 1st page of " chemistry circular " the 10th phase in 1994) be arranged, but they are as the lithium secondary battery electrode material, its reversible lithium storage Capacity Ratio is lower, does not all surpass classical graphite and inserts compound L iC
6Theoretical reversible lithium storage capacity 372mAh/g.And its heat treatment temperature is very high, and great majority are higher than 2000 ℃, and this is comparison difficulty, particularly industrialization on technology.
Electrochemistry can will (J.Electrochem.Soc.) be rolled up the carbon negative pole material that the lithium secondary battery of nitrogenous element reported in the 4th phase 900 pages of one piece of articles delivering in 1994 141.This material with carbon element is unbodied.From X-radiation absorption spectrum, carbon atom X-radiation absorption spectrum is made up of two parts: 285eV and be higher than the part of 295eV, and the former is actually the electron binding energy on the carbon atom ls track; The X-radiation absorption spectrum of its nitrogen-atoms also is made up of two parts simultaneously: 395eV and 405eV, the former is actually the electron binding energy on the nitrogen-atoms ls track.The lithium secondary battery carbon negative pole material of its gained causes the rising of the irreversible capacity of carbon negative pole material on the one hand, the insertion current potential of lithium is reduced, make lithium when inserting, form dendrite easily like this, thereby can cause battery short circuit, thereby think that nitrogenous material with carbon element is not suitable for the carbon negative pole material as lithium secondary battery.
The objective of the invention is to overcome heat treatment temperature height in the prior art (more than 2000 ℃) and the low shortcoming of its reversible lithium storage capacity, obtained the high lithium secondary battery carbon negative pole material of reversible lithium storage capacity.
Another object of the present invention is for introducing nitrogen-atoms in the carbon negative pole material of lithium secondary battery, make the nitrogenous lithium secondary battery carbon negative pole material of gained not only can not cause the rising of irreversible capacity and the reduction of inserting current potential, can cause the rising of reversible lithium storage capacity on the contrary.
The carbon negative pole material of the lithium secondary battery of gained of the present invention comprises amorphous carbon material, conductive carbon black, and adhesive, its composition and content are as follows: (weight portion)
100 parts of amorphous carbon materials
Conductive carbon black 0-10 part
Adhesive 0.5-8 part
The interlamellar spacing of this amorphous carbon material is measured with the X-powder diffraction method, the interlamellar spacing d that records
002Be positioned at 3.34A
0-3.75A
0Its N/C atomic ratio, H/C atomic ratio and O/C atomic ratio CHN-rapid analysis method, measured N/C atomic ratio scope is 0.0-0.9, preferable range is 0.0-0.4; H/C atomic ratio scope is 0-0.5, and preferable range is 0.1-0.3; O/C atomic ratio scope is 0-0.3.The Is orbital electron binding energy of the amorphous carbon material carbon atom of gained is measured with the XPS analysis method, the Is orbital electron of the amorphous carbon material carbon atom that records is made up of three parts in conjunction with power spectrum, promptly is positioned at 288.4eV-287.4eV scope, 286.8eV-285.8eV scope and 285.4eV-284.0eV scope; During the nitrogenous element of gained amorphous carbon material, the electron binding energy of the ls track of the nitrogen-atoms of this amorphous carbon material spectrum is made up of two parts, promptly is positioned at 401.3eV-400.3eV scope and 399.0eV-398.0eV scope; When the gained amorphous carbon material contained oxygen element, the electron binding energy of the ls track of the oxygen atom of this amorphous carbon material spectrum promptly was positioned at 534.5eV-533.5eV scope and 532.5eV-531.5eV scope by two parts.
The carbon negative pole material of lithium secondary battery of the present invention comprises the cleavage method of polymer, and this preparation methods is undertaken by following sequential steps:
1, the preparation of indefiniteness material with carbon element: linearity or crosslinked macromolecule is placed the stove that can ventilate, in certain atmosphere or under low temperature range 400-1500 ℃, carrying out cracking or heat treatment under the vacuum, in the time of staying of cracking or heat treated topnotch is 1 minute-24 hours, obtains the amorphous carbon material of macromolecule cracking.The amorphous carbon material of the macromolecule cracking of above-mentioned gained pulverized be the particle of particle size 20 μ m-2 μ m.
2, the preparation of carbon negative pole material: with the adhesive of the conductive carbon black of amorphous carbon material after the pulverizing of above-mentioned gained and 0-10%, 0.5-8% such as polytetrafluoroethylene, polyethylene, polypropylene, polyethylene propylene, Kynoar etc., evenly mix, extruding in flakes on collector electrode; Can certainly in appropriate solvent, become suspension, on collector electrode, smear then, dry in flakes.The sheet material of gained is in a vacuum in 100-250 ℃ of drying.The sheet material of dry like this back gained just can be used as the carbon negative pole material of lithium secondary battery, can be in the argon gas case of anhydrous and oxygen-free or anhydrous environment be assembled into lithium ion battery, also can be assembled into the double ion battery with the positive pole of double ion battery with the positive pole of lithium ion battery.
Linear polymeric described in the said method can be polystyrene, polyvinyl chloride, Vingon, linear phenolic resin, polyacrylonitrile, polyvinyl pyridine, polyamide, polypyridine, polypyrrole, polyvinyl pyridine, polyaniline etc.; Cross-linked polymer described in the said method can be crosslinked phenolic resins, the polystyrene of using divinylbenzene crosslink, aniline amine aldehyde resin, Lauxite, ethyl-amine resin, polyimides, use the polyacrylonitrile of divinylbenzene crosslink etc.
The described atmosphere of said method can be inert atmosphere, as nitrogen, argon gas etc.; Can be earlier oxidizing atmosphere also, the back be the inert atmosphere of as above saying.
The cryogenic temperature scope of said method is preferably 500-1000 ℃.The maximum temperature time of staying in cracking is preferably 0.1-10 hour, more preferably 0.5-5 hour.
Press the carbon negative pole material of the lithium secondary battery of gained of the present invention, method that it is more traditional such as chemical gaseous phase deposition method want high at the reversible lithium storage capacity of the prepared carbon negative pole material of same condition; Simultaneously after having introduced nitrogen-atoms, the reversible lithium storage capacity of the nitrogenous carbon negative pole material of gained is not only more introduced the reversible lithium storage capacity of the carbon negative pole material of nitrogen-atoms and is wanted high, and broken through the highest reversible lithium storage capacity 372mAh/g of classical graphite material, can be up to more than the 536mAh/g.
So the carbon negative pole material of the lithium secondary battery of gained of the present invention, because the more aforesaid traditional method temperature of its cracking temperature is low, so easy industrialized production.
Below provide the part specific embodiment for the purpose of understanding for the present invention.Providing of these embodiment limits the present invention anything but.
Embodiment 1,
With the macromolecule polysterol of linearity, place a pyrolysis oven, earlier logical Ar gas makes it become inert atmosphere, is warming up to 600 ℃ then, at 600 ℃ of cracking 1 hour, cool to room temperature then.Analyze the constituent content of resulting polymers cracking carbon, see Table 1.XPS data and interlamellar spacing d
002Divide and to see Table 2 and table 3.
Grind resulting polymers cracking carbon, cross the sieve of 10 μ m.The polymer cracking carbon that sieved and 5% conductive carbon black, 3% polytetrafluoroethylene are mixed, and extruding in flakes on collector electrode.After the vacuumize, just can be used for the carbon negative pole material of lithium secondary battery.
The method of testing of the reversible lithium storage capacity of the carbon negative pole material of gained is as follows:
Carbon negative pole material and metal lithium sheet with above-mentioned gained in the argon gas case of anhydrous and oxygen-free are assembled into battery, the barrier film of this battery be porous polypropylene, electrolyte be in 7: 3 EC of volume ratio and the DEC mixture every liter be dissolved with 1 mole of LiClO
4Solution, the battery of being formed discharges and recharges in the scope of 2.0V--0.03V, and the current constant that discharges and recharges is 20mA/g.Its measured reversible lithium storage capacity example is in table 4.
Embodiment 2,
Poly--4-vinylpyridine is used with embodiment 1 identical method and operation and carried out cracking, the result of the constituent content of resulting polymers carbon, XPS analysis gained and interlamellar spacing d
002Divide see Table 1, table 2 and table 3.The test of its reversible lithium storage capacity is as described in the embodiment 1, and measured reversible storage capacity sees 4.
Embodiment 3,
With the foregoing description 1 described method, polyacrylonitrile is carried out cracking, the result of the constituent content of resulting polymers carbon, XPS analysis gained and interlamellar spacing d
002Divide see Table 1, table 2 and table 3.The test of its reversible lithium storage capacity is as described in the embodiment 1, and measured reversible lithium storage capacity sees 4.
Embodiment 4,
With the foregoing description 1 described method, ethyl-amine resin is carried out cracking, the constituent content of resulting polymers carbon, the result of XPS analysis and interlamellar spacing d
002Divide see Table 1, table 2 and table 3.And dress up lithium rechargeable battery according to same operational group.The test of its reversible lithium storage capacity is as described in the embodiment 1, and measured reversible lithium storage capacity sees 4.
Embodiment 5,
With the identical method of the foregoing description 1, with ethyl-amine resin the temperature that is different from embodiment 1 promptly 800 ℃ heat-treat, other condition and operation are with embodiment 1.The constituent content of the polymer cracking carbon of gained, the result of XPS analysis and interlamellar spacing d
002Divide see Table 1, table 2 and table 3.The test of its reversible lithium storage capacity is as described in the embodiment 1, and measured reversible lithium storage capacity sees 4.Comparative Examples,
At 600 ℃ of cracking benzene gas, catalyst for cracking is Ni and Fe alloy with chemical vapour deposition technique.The constituent content of gained chemical vapor carbon deposition, the result of XPS analysis and interlamellar spacing d
002Divide see Table 1, table 2 and table 3.The test of its reversible lithium storage capacity is as described in the embodiment 1, and measured reversible lithium storage capacity sees 4.
N/C, the H/C of table 1 gained material with carbon element and the atomic ratio of O/C
| The example name | The N/C atomic ratio | The H/C atomic ratio | The O/C atomic ratio |
| Embodiment 1 | 0．00429 | 0．0209 | |
| Embodiment 2 | 0．0804 | 0．0439 | 0．0251 |
| Embodiment 3 | 0．178 | 0．351 | 0．0712 |
| Embodiment 4 | 0．217 | 0．241 | 0．240 |
| Embodiment 5 | 0．0673 | <0．04 | 0．0540 |
| Comparative Examples | <0．04 |
The electron binding energy position of table 2 gained material with carbon element
| The example name | C lsBinding energy (eV) | N lsBinding energy (eV) | O lsBinding energy (eV) |
| Embodiment 1 | 288．3(6．68)， 286．7(17．18)， 285．3(76．14) | 533．8(70．0) 532．1(30．0) | |
| Embodiment 2 | 287．4(10．45)， 285．8(17．0)， 284．5(72．55) | 400．5(52．7)， 398．3(47．3) | 534．2(24．0)， 532．1(76．0) |
| Embodiment 3 | 287．6(9．25)， 286．2(15．6)， 284．5(75．1) | 400．1(53．5)， 398．2(46．5) | 533．5(31．1)， 531．9(68．9) |
| Embodiment 4 | 288．1(7．32)， 286．4(31．3)， 285．0(61．4) | 401．0(48．4)， 399．8(51．6) | 533．9(49．8)， 532．0(50．2) |
| Embodiment 5 | 287．8(9．13)， 286．3(10．1)， 285．0(75．3) | 401．3(65．8)， 398．9(34．2) | 533．8(49．8)， 531．8(42．9) |
| Comparative Examples | 288．4(3．52)， 286．6(8．83)， 285．3(87．6) |
Annotate: in the bracket is relative percentage composition.
The interlamellar spacing size of table 3 gained material with carbon element
| The example name | d 002Size (A 0) |
| Embodiment 1 | 3．489 |
| Embodiment 2 | 3．550 |
| Embodiment 3 | 3．552 |
| Embodiment 4 | 3．434 |
| Embodiment 5 | 3．476 |
| Comparative Examples | 3．477 |
The reversible lithium storage capacity of table 4 gained material with carbon element
| The example name | Reversible lithium storage capacity (mAh/g) |
| Embodiment 1 | 345 |
| Embodiment 2 | 382 |
| Embodiment 3 | 435 |
| Embodiment 4 | 536 |
| Embodiment 5 | 400 |
| Comparative Examples | 275 |
From table 4, know, want high than the material with carbon element of usual way such as chemical vapour deposition technique preparation according to the capacity of the reversible insertion lithium ion of the material with carbon element of method gained of the present invention.According to the present invention's (contrast of embodiment 1 and embodiment 2, embodiment 3, embodiment 4 and embodiment 5) the nitrogen element is incorporated in the material with carbon element simultaneously, the structure of the material with carbon element of gained is different from reported on the aforesaid J.Electrochem.Soc, this can find out fully from the electron binding energy of carbon atom ls track and the electron binding energy of nitrogen-atoms ls track.Therefore the reversible lithium storage capacity of the lithium secondary battery carbon negative pole material of gained of the present invention does not only cause the reduction of irreversible lithium storage content, and the storage lithium reversible capacity of material with carbon element is improved, and also breaks through the classical theory capacity 372mAh/g of graphite.
The material with carbon element of gained of the present invention can be used as the negative pole of high lithium ion battery of energy density and double ion battery.
Claims (7)
1, lithium secondary battery carbon negative pole material is characterized in that described carbon negative pole material comprises following component and content (weight portion)
100 parts of amorphous carbon materials
Conductive carbon black 0-10 part
The described amorphous carbon material interlamellar spacing of adhesive 0.5-8 part d
002Be 3.434-3.552, described adhesive is a polytetrafluoroethylene.
2, lithium secondary battery carbon negative pole material according to claim 1 is characterized in that the N/C atomic ratio is 0.06-0.21 in the described amorphous carbon material.
3, lithium secondary battery carbon negative pole material according to claim 1 is characterized in that the H/C atomic ratio is 0.004-0.35 in the described amorphous carbon material.
4, lithium secondary battery carbon negative pole material according to claim 1 is characterized in that the O/C atomic ratio is 0.02-0.24 in the described amorphous carbon material.
5, the manufacture method of lithium secondary battery carbon negative pole material according to claim 1 is characterized in that being undertaken by following sequential steps:
(1) preparation of amorphous carbon material
With linearity or cross-linked polymer place the stove that can ventilate, under nitrogen or argon gas atmosphere or vacuum, under low temperature range 400-1500 ℃, carried out cracking or heat treatment 1 minute-24 hours, be ground into the particle of 20 μ m-2 μ m.
(2) preparation of carbon negative electrode: with the conductive carbon black of amorphous carbon material after the pulverizing of above-mentioned gained and 0-10%, the adhesive of 0.5-8% evenly mixes, and extruding in flakes on collector electrode.
6, the manufacture method of lithium secondary battery carbon negative pole material according to claim 5 is characterized in that described linear polymeric is polystyrene, polyvinyl chloride, Vingon, polyvinyl pyridine, polyacrylonitrile, polyamide, polypyridine or polyaniline.
7, the manufacture method of lithium secondary battery carbon negative pole material according to claim 5, it is held to levy and is that described cross-linked polymer is phenolic resins, ethyl-amine resin or polyimides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96114133A CN1061472C (en) | 1996-12-25 | 1996-12-25 | Carbon material for cathode of lithium secondry battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96114133A CN1061472C (en) | 1996-12-25 | 1996-12-25 | Carbon material for cathode of lithium secondry battery |
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|---|---|
| CN1186353A CN1186353A (en) | 1998-07-01 |
| CN1061472C true CN1061472C (en) | 2001-01-31 |
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| CN96114133A Expired - Fee Related CN1061472C (en) | 1996-12-25 | 1996-12-25 | Carbon material for cathode of lithium secondry battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4789330B2 (en) * | 2001-02-22 | 2011-10-12 | 株式会社クレハ | Non-aqueous solvent secondary battery electrode material, electrode and secondary battery |
| CN114824165B (en) * | 2022-06-30 | 2022-10-14 | 宁德新能源科技有限公司 | Negative electrode plate, electrochemical device and electronic equipment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053513A (en) * | 1991-03-05 | 1991-07-31 | 复旦大学 | With the complex Li-Mn-oxide is anodal all solid-state lithium battery |
| EP0652602A2 (en) * | 1993-09-30 | 1995-05-10 | Sumitomo Chemical Company, Limited | Lithium secondary battery |
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- 1996-12-25 CN CN96114133A patent/CN1061472C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1053513A (en) * | 1991-03-05 | 1991-07-31 | 复旦大学 | With the complex Li-Mn-oxide is anodal all solid-state lithium battery |
| EP0652602A2 (en) * | 1993-09-30 | 1995-05-10 | Sumitomo Chemical Company, Limited | Lithium secondary battery |
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| CN1186353A (en) | 1998-07-01 |
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