CN1042875C - Anodes of lithium batteries and manufacture thereof - Google Patents
Anodes of lithium batteries and manufacture thereof Download PDFInfo
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- CN1042875C CN1042875C CN96100810A CN96100810A CN1042875C CN 1042875 C CN1042875 C CN 1042875C CN 96100810 A CN96100810 A CN 96100810A CN 96100810 A CN96100810 A CN 96100810A CN 1042875 C CN1042875 C CN 1042875C
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- anode
- disperse
- active material
- lithium
- lithium battery
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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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Abstract
The present invention belongs to the technical field of a high energy battery, particularly to the technical field of preparing an anode of a lithium battery or a lithium ion battery at room temperature. The present invention aims to improve the specific capacity of anode material of the lithium battery, increase battery energy density and increase mechanical chemical stability of an anode. Thus, a dispersing anode for a lithium battery is provided, and the dispersing anode is prepared by that active substances which account for 80 to 99 wt% are mixed with dispersant which accounts for 20 to 1 wt% by a physical method, the mixture is refined, or after the mixture is further dispersed, a membrane is prepared, and the membrane is dried in vacuum. The preparation method provided by the present invention is simple, and is easy for industrial production.
Description
The invention belongs to the high-energy battery technical field, particularly make the technical field of room temperature lithium battery or lithium ion battery anode.
Lithium metal and various lithium alloy such as lithium-aluminium alloy, lithium silicon alloy, Li-Pb alloy, lithium boron alloy, lithium ferroalloy, lithium-tin alloy and be the anode material that the lithium alloy etc. of base can become lithium battery with the Wood's metal.The battery that constitutes by them, because of the surperficial dendritic growth of its anode, the influence of factors such as mechanical instability and chemical instability, the life-span of its charge and discharge cycles is very short.As list of references: [1] K.M.Abraham, Electro-chemica Acta.138, described in 1233 (1993).
In addition, the embedding compound of some lithiums can also be as the anode of lithium battery, and this class battery is called as lithium ion battery.Embedding compound anode does not have the problem of dendritic growth, and its mechanical stability and chemical stability are improved, and cycle life obtains increasing.The cycle life that with the material with carbon element is the lithium ion battery of anode can reach thousands of times, also report to some extent in the document 1.Present commercial lithium ion battery mainly is being anode through the carbon material or the graphite of special processing.The graphite degree of changing into of the carbon material of process special processing is different, and its theoretical capacity is generally less than desirable graphite material.One mole of desirable graphite (C
6) multipotency embeds a mole of lithium (Li), its theoretical specific capacity is 372mAh/g, theoretical specific capacity 3830mAh/g well below pure metal lithium, also be lower than the specific capacity 790mAh/g of some lithium alloy such as lithium-aluminium alloy, thereby the energy density of lithium ion battery is far below the lithium battery of making anode with pure metal lithium.
The objective of the invention is to increase by two alternate interfaces, become the embedded location of lithium ion, improve the specific capacity of anode material, thereby increase the energy density of battery.Second purpose of the present invention also is to utilize multi phase interface, absorbs and be released in lithium ion to embed and go the stress that crystal grain produces in the embedding process, to increase the mechanical stability and the chemical stability of anode.This anode has improved the efficiency for charge-discharge of battery and has reduced the fall off rate of battery capacity.With physical method active material is accounted for 80-99wt% and mix through ultra-fineization thereby provide a kind of, or further make film after the disperseization, become the disperse anode that is used for lithium battery through vacuumize with the disperse means of 20-1wt%.The present invention adopts physical method that raw material is mixed, make superfines by mechanical lapping, Ultrasonic Pulverization etc., particle size is 40-0.001mm, perhaps more further the powder disperseization of ultra-fineization (two step once finish also can), method such as repressed or evaporation, sputter, discharge, spraying is made film the powder of ultra-fineization, becomes the anode material that is used for lithium battery through vacuum drying treatment again.Consisting of of disperse phase anode provided by the invention:
Disperse anode=nonactive medium the B of x{y active material A1+ (1-y) active material A2}+ (1-x);
Its content of x accounts for the 80-99wt% of total amount for active material A1+A2, and wherein A1 accounts for the 1-99wt% of active material total amount again; Surplus is A2;
Wherein active material A1 is first phase, be can the embedding lithium compound, comprising: graphite (artificial, natural), through various carbon materials such as petroleum coke, middle phase charcoal microballon, carbon fiber and the polymer etc. of appropriate heat treatment and embed compound such as TiS
2, Li
3-xM
xN (M=transiting group metal elements Ni, CO, Cu, O＜x＜1), LiTi
2O
4, BC
2N.
Active material A2 is second phase, is the metal or alloy that can form alloy with lithium, or compound that can the embedding lithium.Metal or alloy comprises: metal and the mutual alloys that form thereof such as Al, Sb, Bi, Si, Sn, Ga, In, Cd, Zn, Pb, Mg, Fe, and the alloy of these metal or alloy and Li formation.
B is disperse means, comprising: binding agents such as polytetrafluoroethylene, Kynoar and the second third lemon glue.Its disperse means content accounts for the 20-1wt% of total amount.
In the disperse phase anode provided by the invention, the effect of active material first phase is the embedding main body of lithium.Active material second is divided by as outside the active material, can also produce active material (one or both) interface or increase the surface of active material, from but the quick transmission channel of lithium ion.Another effect of second phase is the buffer that serves as the change in volume of active material (or another kind of active material), alleviate active material in charge and discharge process since the change in volume that volumetric expansion or contraction or phase transformation produce to the harmful effect of battery life.The effect of disperse means is with active material first mutually and second mutually and the anode substrate tight bond, the strip of formation even dispersion.
The capacity of disperse phase anode provided by the invention also can embed the theoretical specific capacity 372mAh/g of compound L iC6 greater than the one-level of graphite greater than the capacity 200mAh/g of present widely used carbon material.Disperse phase anode provided by the invention can suppress electrolytical decomposition in the charge and discharge cycles process.Can prepare lithium battery or the lithium ion battery that satisfies various household electrical appliance requirements with disperse phase anode provided by the invention, also can prepare and be suitable for high power lithium battery or the lithium ion battery that electric automobile and energy storage are used.Preparation method provided by the invention is simple, is easy to suitability for industrialized production.
Below in conjunction with embodiment the present invention is described in further detail: it is graphous graphite powder (spectroscopic pure) that embodiment 1 adopts the active material first phase A1, the active material second phase A2 is aluminium powder (analyzing pure), active material A1+A2 accounts for the 95wt% of total amount, and its surplus is 5wt% for the poly-tetrafluoro powder (analyzing pure) of disperse means B; Active material A1 and A2 account for the 20wt% (A1) and the 80wt% (A2) of active material total amount separately.Three kinds of raw materials are placed in the agate mortar ground 3 hours.Depressing to diameter at the pressure of 10MPa is that 10 millimeters, thickness are the thick film of 60-120 micron, under the 140-240 temperature vacuumize 20-100 hour.The charging reversible specific capacity that records the electrode of this thick film work is 500-640mAh/g.The folded powder (spectroscopic pure) of embodiment 2 artificial stones be A1, and lithium-aluminium alloy (analyze pure, the weight content of the lithium in the alloy is 13%) is A2, and Kynoar (analyzing pure) is B, and its content is x=97wt%, y=12wt%.Behind ball milling 8hr mixing, on Copper Foil, evenly paint the thick film of thick 20-100 micron, through 150-200 temperature vacuumize 20-60 hour, as the anode of lithium ion battery.Its efficiency for charge-discharge reaches 80-85%.Embodiment 3 is with plain powder (A1) of charcoal and Kynoar (B) mixing, and making thickness is the porous strip of 20-100mm, with vacuum vapour deposition zinc (A2) is permeated into the porous strip under the vacuum degree of 10-2-10-5Pa, the disperse phase anode.Form: x=96wt%, y=98wt%.Its reversible capacity is 300-400mAh/g.Embodiment 4 acicular petroleum cokes (technical pure) are A1, and Delanium (spectroscopic pure) is A2, and poly-tetrafluoro (analyzing pure) is B, and its content is x=96wt%, y=70wt%.Underhand polish 3hr in agate mortar.Depressing to diameter at the pressure of 10MPa is that 10 millimeters, thickness are the thick film of 40-140 micron, under 160-240 ℃, and vacuumize 24-96 hour.Its reversible capacity is 240-280mAh/g, and capacity is very little with the decay of cycle-index.Embodiment 5 A1 are the plain powder of charcoal (analyzes pure, 93 microns), and A2 is Si powder (analyzes pure, 93 microns), behind the grinding mixing, again with the Kynoar mixing, makes the thick disperse phase anode of 30-120mm with common sputtering method.It consists of x=98wt%, y=98wt%.Its specific capacity is greater than 320mAb/g.Embodiment 6 A1 are the plain powder of the charcoal of 98wt% (analyzes pure, 93 microns), and A2 is BixPbyCdzSnw alloy (x+y+z+w=1, x=0-0.6, y=0-0.6, z=0-0.4w=0-0.8) (analyze pure, 93 microns are sieved), the grinding mixing of 2wt%.Be 98wt% by (A1+A2) again, the ratio mixing of Kynoar 2wt% is made the thick disperse phase anode of 40-100mm with common spraying process.Its specific capacity is 300-400mAh/g.Embodiment 7 A1 are the plain powder of the charcoal of 95wt% (analyze pure, 93 microns), and A5 is the Li of 2wt%
3-xM
xN (M is a transition metal, as Co) grinds mixing.Be 98wt% by (A1+A2) again, the ratio mixing of Kynoar 2wt% is made the thick disperse phase anode of 40-100mm with rubbing method.Its specific capacity is 300-450mAh/g.
Claims (6)
1. disperse anode that is used for lithium battery, it is characterized in that comprising at least the form composition of the above active material of two-phase by x{y active material A1+ (1-y) active material A2}+ (1-x) disperse means B, active material weight accounts for the 99-80wt% of total content, and the percentage that disperse means account for total content is 1-20wt%;
Wherein active material A1 is the compound of embedding lithium: graphite, and through heat treated carbon materials, content accounts for the 1-99wt% of whole active materials;
Wherein active material A2 is the metal or metal alloy that forms alloy with lithium, comprise: Al, Sb, Bi, Si, Sn, Ga, In, Cd, Zn, Pb, Mg, Fe metal and the alloy that forms mutually thereof, and the alloy of these metal or alloy and Li formation, the content of active material A2 accounts for the 99-1wt% of whole activity substance contents;
Wherein disperse means B comprises: polytetrafluoroethylene, Kynoar or ethylene-propylene rubber.
2. by the described disperse anode that is used for lithium battery of claim 1, it is characterized in that: the heat treated carbon materials of described process comprises: petroleum coke, middle phase charcoal microballon or carbon fiber, or the embedding compound comprises: TiS
2, Li
3-xM
xN, LiTi
2O
4Or BC
2N; Li wherein
3-xM
xM among the N is transiting group metal elements Ni, Co or Cu, wherein 0＜x＜1.
3. by the described disperse anode that is used for lithium battery of claim 1, it is characterized in that: used material powder adopts other purity of chemical pure higher level, and the granularity scope of its ultra-fineization is 40-0.001mm.
4. one kind prepares by the described method that is used for the disperse anode of lithium battery of claim 1, it is characterized in that: use mechanical lapping, Ultrasonic Pulverization means ultra-fineization of raw material, reach disperseization, its granularity is 40-0.001mm, make film through physical method again, under 140-250 ℃, made the disperse anode film in vacuumize 20-100 hour.
5. the method that is used for the disperse anode of lithium battery by the described preparation of claim 4, it is characterized in that: the powder after ultra-fineization is made film through physical method, comprise pressurization film forming band, after adopting evaporation, sputter, discharge or spraying method to make the disperse phase film, became the disperse anode in vacuumize 20-100 hour.
6. the disperse anode method that is used for lithium battery by claim 4 or 5 described preparations, it is characterized in that: describedly add that to be pressed into the film band be that the compacting thickness is the film of 60-120 micron under the pressure of 10Mpa, and under 140-240 ℃ of temperature vacuumize 20-100 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96100810A CN1042875C (en) | 1996-01-22 | 1996-01-22 | Anodes of lithium batteries and manufacture thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96100810A CN1042875C (en) | 1996-01-22 | 1996-01-22 | Anodes of lithium batteries and manufacture thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1155765A CN1155765A (en) | 1997-07-30 |
| CN1042875C true CN1042875C (en) | 1999-04-07 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96100810A Expired - Fee Related CN1042875C (en) | 1996-01-22 | 1996-01-22 | Anodes of lithium batteries and manufacture thereof |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1050940C (en) * | 1998-01-09 | 2000-03-29 | 浙江大学 | Carbon based composite material for cathode of lithium ion secondary battery and manufacture thereof |
| KR100529070B1 (en) * | 2003-01-29 | 2005-11-16 | 삼성에스디아이 주식회사 | Method of preparing rechargeable lithium battery |
| CN101420023B (en) * | 2008-12-11 | 2010-06-09 | 浙江大学 | Electrochemical lithium ionic insertion/deinsertion electrode and production method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5219680A (en) * | 1991-07-29 | 1993-06-15 | Ultracell Incorporated | Lithium rocking-chair rechargeable battery and electrode therefor |
| US5366829A (en) * | 1993-06-14 | 1994-11-22 | Valence Technology, Inc. | Method of forming an anode material for lithium-containing solid electrochemical cells |
| WO1995007551A1 (en) * | 1993-09-10 | 1995-03-16 | Hyperion Catalysis International, Inc. | Lithium battery with electrodes containing carbon fibrils |
-
1996
- 1996-01-22 CN CN96100810A patent/CN1042875C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5219680A (en) * | 1991-07-29 | 1993-06-15 | Ultracell Incorporated | Lithium rocking-chair rechargeable battery and electrode therefor |
| US5366829A (en) * | 1993-06-14 | 1994-11-22 | Valence Technology, Inc. | Method of forming an anode material for lithium-containing solid electrochemical cells |
| WO1995007551A1 (en) * | 1993-09-10 | 1995-03-16 | Hyperion Catalysis International, Inc. | Lithium battery with electrodes containing carbon fibrils |
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|---|---|
| CN1155765A (en) | 1997-07-30 |
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