CN103715394A - Lithium ion battery anode and preparation method thereof - Google Patents
Lithium ion battery anode and preparation method thereof Download PDFInfo
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- CN103715394A CN103715394A CN201310692645.1A CN201310692645A CN103715394A CN 103715394 A CN103715394 A CN 103715394A CN 201310692645 A CN201310692645 A CN 201310692645A CN 103715394 A CN103715394 A CN 103715394A
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title abstract description 14
- 239000011521 glass Substances 0.000 claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000758 substrate Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 9
- 239000002238 carbon nanotube film Substances 0.000 claims description 65
- 239000005030 aluminium foil Substances 0.000 claims description 52
- 239000011248 coating agent Substances 0.000 claims description 48
- 238000000576 coating method Methods 0.000 claims description 48
- 239000002041 carbon nanotube Substances 0.000 claims description 37
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 37
- 239000000463 material Substances 0.000 claims description 16
- 239000007774 positive electrode material Substances 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 238000004513 sizing Methods 0.000 claims description 13
- 239000002002 slurry Substances 0.000 claims description 13
- 238000003466 welding Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000006258 conductive agent Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000006245 Carbon black Super-P Substances 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 239000004411 aluminium Substances 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- -1 after fixing Substances 0.000 claims description 4
- 238000007755 gap coating Methods 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 238000009434 installation Methods 0.000 claims description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- DJZIBVUGARDLOC-UHFFFAOYSA-N [Ni]=O.[Co]=O.[Li] Chemical compound [Ni]=O.[Co]=O.[Li] DJZIBVUGARDLOC-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 239000012528 membrane Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000011888 foil Substances 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract 8
- 239000010405 anode material Substances 0.000 abstract 5
- 238000010586 diagram Methods 0.000 description 5
- 238000005520 cutting process Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000000873 masking effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- 208000032953 Device battery issue Diseases 0.000 description 1
- 244000141353 Prunus domestica Species 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/50—Current conducting connections for cells or batteries
- H01M50/531—Electrode connections inside a battery casing
-
- 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 discloses a lithium ion battery anode and a preparation method thereof. The anode utilizes a carbon nano pipe film formed by a carbon nano pipe macroscopic pipe as a current collector, and an anode material layer is formed on the carbon nano pipe film. Compared with the traditional aluminum foil current collector anode, the lithium ion battery anode has the advantages that the weight of the lithium ion battery anode prepared by the method is light, and the anode material layer and the current collector are firmly combined. The preparation method comprises the following steps of preparing a high strength carbon nano pipe on a glass substrate by utilizing a carbon nano pipe macroscopic pipe continuum generated by a reactor port, generating the anode material layer on the carbon nano pipe film layer, separating the carbon nano pipe film layer with the anode material layer from and the glass substrate, and mounting a pole ear on a pole piece. Under the same size, the carbon nano pipe film is far lighter than the aluminum foil, the weight of the saved part can be replaced by the anode material, and the capacity of the battery is 15%-50% higher than that of a battery which takes the aluminum foil as an anode current collector. The lithium ion battery anode is low in cost, high in generation efficiency, simple in equipment, capable of realizing semicontinuous operation and suitable for mass production.
Description
Technical field
The present invention relates to battery manufacture technical field, relate in particular to a kind of lithium ion cell positive and preparation method thereof.
Background technology
At the current most popular power supply of field of mobile equipment, surely belong to lithium ion battery, its major part comprises positive pole, negative pole, barrier film, electrolyte and shell body.Wherein, electrode fabrication is the core technology in lithium ion battery manufacture process, and positive pole comprises plus plate current-collecting body (containing lug) and is evenly formed on the positive electrode material layer of collection liquid surface.The Weak current that active particle in electrode material layer produces need be brought together with larger current forms and be exported to external circuit by collector, and lug can coordinate collector from battery core, both positive and negative polarity to be caused to external circuit better.At present, lithium ion battery generally adopts aluminium foil as plus plate current-collecting body, the good conductivity of aluminium, be easily processed into paper tinsel, mechanical strength feature good, relative low price is used it in a large number.Along with the extensive use of lithium ion battery, people have higher requirement for battery: quality is lighter, energy is higher, environmental protection more.Yet, aluminium foil as plus plate current-collecting body for the capacity of battery without any contribution, its quality but accounts for 15% left and right of whole positive pole, this will reduce the energy density of battery greatly.In addition, because adhesion between positive electrode material layer and aluminium foil is not strong, occur that the situation of dry linting happens occasionally, cause battery performance to worsen.
Carbon nano-tube is a kind of novel nano material, the geometry that it is unique and electronic band structure, make it have excellent electric property, add the low-density far below aluminium, macroscopical film that carbon nano-tube gathering forms is expected to substitute aluminium foil becomes lithium ion cell positive collector of new generation.
Through the literature search of prior art is found, to the research of carbon nano-tube collector at present also in the research and probe stage.
The Ke Wang of Tsing-Hua University, Shu Luo, at the < < Super-Aligned Carbon Nanotube Films as Current Collectors for Lightweight and Flexible Lithium Ion Batteries > > of < < Advanced Functional Materials > > (advanced function material) the 23rd phase 846-853 page in 2013, (super even carbon nano-tube film is used as lightweight as collector to Yang Wu etc., pliable and tough lithium ion battery) in a literary composition, propose with carbon nano-tube film as lithium ion battery plus-negative plate collector.The people such as the Wang Jiaping of Tsing-Hua University, Wang Ke have set forth the manufacture craft of the electrode of carbon nano-tube film collector in the national inventing patent (CN 103187574 A) of its application.The work that they do has illustrated that it is possible that carbon nano-tube film alternative metals is served as collector well.This allows people from a new angle---the energy density of lithium ion battery is gone to improve in collector aspect, is no longer confined to electrode material.Yet due to the method problem of making at present, there is the deficiency of following several times in carbon nano-tube film collector: (1) masking efficiency is low, the size-constrained system of film, mechanical strength is not high; (2) although can connecting tab, yet with conducting resinl connecting tab and collector, the conducting resinl of introducing has not only increased the weight of pole piece, conducting resinl long period of soaking is easily aging in electrolyte simultaneously; (3) in electrode fabrication process, be first to form electrode material layer, then on electrode material layer, form carbon nano-tube rete, this make with traditional lithium ion battery on collector the technique of coating electrode pulp layer to compare variation too large, if be used in actual production, mean that manufacturer needs the extensive production line of adjusting, cost is too high.
Summary of the invention
The invention provides a kind of high efficiency, high-quality based on carbon nano-tube film, and lithium ion cell positive preparation method easy and that existing cell making process integrates with.
The present invention adopts following technical scheme:
It is collector that lithium ion cell positive of the present invention be take the carbon nano-tube film that carbon nano-tube macroscopic pipe forms, and positive electrode material layer is formed on carbon nano-tube film; Positive plate lug adopts the form of biplate aluminium foil folder carbon nano-tube film, and realizes electrical connection by spot welding.This carbon nano-tube film surface density is lower than 1.0 * 10
-3gcm
-2, mechanical strength is 100-150Mpa.
The manufacture method of the New Type of Carbon nanotube films collector the present invention relates to, the method is applicable to the positive pole of button cell, cylindrical battery, particularly laminated battery plate and makes, and comprises the steps:
The prepared lithium ion cell positive of method of the present invention is lighter with the anodal phase specific mass of traditional aluminum foil current collector, and positive electrode material layer is combined more firm with collector.Under same size, carbon nano-tube film is far lighter than aluminium foil, and this part quality of saving is replaced to positive electrode, and battery capacity will exceed 15%-50% than take the battery that aluminium foil is plus plate current-collecting body.The present invention is with low cost, and formation efficiency is high, and equipment is simple, can realize semicontinuous operation, is suitable for a large amount of production.
Good effect of the present invention is as follows:
The first, directly the carbon nano-tube macroscopic pipe non-individual body generating from reactor mouth is made to film forming, masking efficiency is high, can prepare in theory the carbon nano-tube film of arbitrary dimension size, and in practical operation, prepared maximum carbon nano-tube film size reaches 1.5m * 2m.
The second, adopt the thin film-forming method of graticules in length and breadth, each carbon nanotube macroscopic view pipe in rete is interlaced, and each carbon nano-tube on microcosmic is interweaved, and the mechanical strength (100-150Mpa) that this film that makes to produce has had, is convenient to later use.
The 3rd, because carbon nano-tube film density is minimum, surface density (10 μ m) < 1.0 * 10
-3gcm
-2much smaller than aluminium foil (20 μ m) 5.44 * 10
-3gcm
-2, use this film collector can effectively reduce the quality of inert matter in whole electrode, thereby can improve simply and effectively the energy density of battery.
The 4th, due to the speciality of carbon nano-tube film rough surface porous and good wetability, its surface is more conducive to slurry to be adhered to, and has strengthened the cohesive force between slurry and collector, is not prone to dry linting phenomenon.
The 5th, the form that lug adopts aluminium foil folder carbon nano-tube film, realizes electrical connection by spot welding.This mode is without being used conducting resinl, and due to the battery failure defect of saving the quality of conducting resinl and having avoided causing because conducting resinl is aging, pole piece quality is lighter simultaneously; Monolithic aluminium foil THICKNESS CONTROL is below 20 μ m, and the thickness of lug part is suitable with positive electrode layer thickness, and guaranteeing can close contact between laminated battery plate positive/negative plate.
Accompanying drawing explanation
Fig. 1 is gap coating schematic diagram
Fig. 2 is the front schematic diagram of aluminium foil lug cutting when lug is positioned at side
Fig. 3 is schematic diagram after the cutting of aluminium foil lug when lug is positioned at side
Fig. 4 is the front schematic diagram of aluminium foil lug cutting when lug is positioned at top
Fig. 5 schematic diagram after the cutting of aluminium foil lug for above lug is positioned at time
1 carbon nano-tube rete, 2 positive electrode material layers, 3 aluminium foil lugs, 4 positive plates.
Embodiment
The following examples are to describe in further detail of the present invention.
The preparation of Snap-type cell positive: spraying upper volume mark on glass substrate (20cm * 20cm) and glass bar is 30% alcohol water blend, draws with glass bar the macroscopic view pipe non-individual body generating from reactor mouth to square glass substrate.Adopt the form of graticules in length and breadth, on glass substrate, will obtain the carbon nano-tube film of thickness approximately 10 μ m.By active material (LiCoO
2), conductive agent (Super-P), binding agent (Kynoar) mix (solid content remains on 45%) with NMP in the ratio of 90:4:6, put into ball mill ball milling 10h, rotating speed 232rmin
-1, obtain anode sizing agent.Keep scraper edge 180 μ m, on film, evenly smear last layer slurry, put into baking oven, 120 ℃, 40min.Subsequently, the glass substrate that is loaded with coating carbon nano-tube rete is kept flat, with hairbrush, dip NMP, at the carbon nano-tube diaphragm area that is not coated with slurry, gently brush.After coating does not partly soak, with blade of carving knife, gently scrape the edge of carbon nano-tube film, make the edge of film separated with glass substrate, after film and glass substrate separating part area can be by clamp clamps, use fixture clamping carbon nano-tube film separating part instead, with 0.5-1cms
-1speed to not separated side, lift, until the carbon nano-tube film that scribbles slurry is separated completely from glass plate.After end to be separated, the carbon nano-tube film that is loaded with material is put into 120 ℃ of baking oven 20min.Be loaded with the carbon nano-tube film of material after roll-in, on perforating press, go out
the disk of 12mm.So far, button cell positive pole just completes.
The preparation of individual layer laminated batteries positive pole: spraying upper volume mark on glass substrate (20cm * 36cm) and glass bar is 30% alcohol water blend, draws with glass bar the macroscopic view pipe non-individual body generating from reactor mouth to square glass substrate.Adopt the form of graticules in length and breadth, on glass substrate, will obtain the carbon nano-tube film of thickness approximately 13 μ m.By active material (LiCoO
2), conductive agent (Super-P), binding agent (Kynoar) mix (solid content 45%) in the ratio of 90:4:6 with NMP, put into ball mill ball milling 12h, rotating speed 232rmin
-1, obtain anode sizing agent.The mode that adopts " the moving film of cutter is fixed ", the glass plate that is loaded with film is motionless, and scraper is with 230 μ m edge of a knife feeds above film, anode sizing agent is coated with on carbon nano-tube film in " gap coating " mode, every coating is of a size of 8cm * 18cm, gap width 4cm, and concrete condition is shown in Fig. 1.After coating finishes, glass plate being placed in to 120 ℃ of baking ovens dries.Afterwards, by coating part not on the wetting carbon nanotube layer of the hairbrush that is moistened with NMP, with blade of carving knife, gently scrape afterwards the edge of carbon nano-tube film, make the edge of carbon nano-tube film separated with glass substrate, after film and glass substrate separating part area can be by clamp clamps, use fixture clamping carbon nano-tube film separating part instead, with 0.5-1cms
-1speed to not separated side, lift, until the carbon nano-tube film that scribbles slurry is separated completely from glass plate.After end to be separated, the carbon nano-tube film that is loaded with material is put into 120 ℃ of baking oven 30min.The film of taking off is cut into 12cm * 20cm(has material part 8cm * 18cm to be positioned at center, and all the other are coating part not), roll-in; After roll-in, pole piece is cut into 4.0cm * 3.0cm, wherein anode sizing agent is of a size of 3.0cm * 3.0cm(residual area and is stayed by making lug).Preprepared aluminium foil (thick 20 μ m) is cut into 0.8cm * 3.5cm, with two aluminium foils, pole piece, coating part is not whole is clipped in the middle, notice that aluminium foil has not covered anode sizing agent layer, on pneumatic spot welding machine, weld, the little aluminium flake and the aluminium foil that by the length with tab, are 1.5cm are again welded together, aluminium foil width is trimmed to the carbon nano-tube film that 0.5cm(aluminium foil includes and also prunes away in the lump).So far, individual layer laminated batteries positive pole just completes.
The preparation of multi-layer stacks anode: spraying upper volume mark on glass substrate (20cm * 36cm) and glass bar is 30% alcohol water blend, draws with glass bar the macroscopic view pipe non-individual body generating from reactor mouth to square glass substrate.Adopt the form of graticules in length and breadth, on glass substrate, will obtain the carbon nano-tube film of thickness approximately 13 μ m.By active material (LiCoO
2), conductive agent (Super-P), binding agent (Kynoar) mix (solid content 45%) in the ratio of 90:4:6 with NMP, put into ball mill ball milling ball milling 12h, rotating speed 248rmin
-1, obtain anode sizing agent.The mode that adopts " the moving film of cutter is fixed ", scraper, with 230 μ m edge of a knife feeds above film, is applied to anode sizing agent gap on carbon nano-tube film, and every coating is of a size of 8cm * 18cm, gap width 4cm, concrete condition is shown in Fig. 1.After coating finishes, glass plate being placed in to 120 ℃ of baking ovens dries.Afterwards, by coating part not on the wetting carbon nanotube layer of the hairbrush that is moistened with NMP, with blade of carving knife, gently scrape afterwards the edge of carbon nano-tube film, make the edge of carbon nano-tube film separated with glass substrate, after film and glass substrate separating part area can be by clamp clamps, use fixture clamping carbon nano-tube film separating part instead, with 0.5-1cms
-1speed to not separated side, lift, until the carbon nano-tube film that scribbles slurry is separated completely from glass plate.After end to be separated, the carbon nano-tube film that is loaded with material is put into 120 ℃ of baking oven 30min.The film of taking off is cut into 12cm * 20cm(has material part 8cm * 18cm to be positioned at center, and all the other are coating part not), roll-in; After roll-in, pole piece is cut into 4.0cm * 3.0cm, wherein anode sizing agent is of a size of 3.0cm * 3.0cm(residual area and is stayed by making lug).Preprepared aluminium foil (thick 20 μ m) is cut into 1.5cm * 2.3cm, with two aluminium foils pole piece 1/2 being clipped in the middle of coating part (laterally) not, see Fig. 4, notice that aluminium foil has not covered anode sizing agent layer, on pneumatic spot welding machine, weld, aluminium foil width is trimmed to " protruding " shape shown in Fig. 5, wherein " protruding " shape upper width 0.8cm.So far, multi-layer stacks anode just completes.
Table 1 is for being assembled into battery performance list after button cell battery by the prepared positive pole of embodiment mono-.As described above, the button cell of made be take lithium sheet as negative pole to the positive plate situation of example one, and barrier film is thick 12 μ m,
the disk of 12mm.After battery standing 24h, carry out electric performance test, through 0.1C(2.75-4.2V) after multiplying power changes into, in identical voltage range, the circulation of 1C multiplying power obtains table 1 data.
The table 1 example one button cell performance list of doing
Table 2 is for being assembled into battery performance list after individual layer laminated batteries by the prepared positive pole of embodiment bis-.As described above, the individual layer laminated batteries of made be take graphite as negative pole (negative pole material size 3.5cm * 3.5cm) to the positive plate situation of example two, and the thick 12 μ m of barrier film used, are of a size of 4.0cm * 4.0cm.After battery standing 24h, carry out electric performance test, through 0.1C(2.75-4.2V) after multiplying power changes into, in identical voltage range, the circulation of 1C multiplying power obtains table 2 data.
The table 2 example two individual layer laminated batteries performance list of doing
From above data, can find out, the present invention is prepared just has good performance, carbon nano-tube film for same size, it is qualitatively far below aluminium foil, if this part quality under carbon nano-tube film is saved replaces to positive electrode, the capacity of battery will exceed 20%-50% than take the battery that aluminium foil is plus plate current-collecting body.
The present invention is simple for process, and product not only can apply in the middle of the making of conventional batteries, more obvious in the effect of flexible foldable field of batteries.Raw material of the present invention is simple and easy to get, with low cost, environmentally safe; Efficiency is high, and equipment is simple, can realize semicontinuous operation, is suitable for a large amount of production.
Although illustrated and described embodiments of the invention, for the ordinary skill in the art, be appreciated that without departing from the principles and spirit of the present invention and can carry out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claims and equivalent thereof.
Claims (10)
1. a lithium ion cell positive, is characterized in that: it is collector that this lithium ion cell positive be take the carbon nano-tube film that carbon nano-tube macroscopic pipe forms, and positive electrode material layer is formed on carbon nano-tube film; Positive plate lug adopts the form of biplate aluminium foil folder carbon nano-tube film, and realizes electrical connection by spot welding.
2. lithium ion cell positive as claimed in claim 1, is characterized in that: this carbon nano-tube film surface density is lower than 1.0 * 10
-3gcm
-2, mechanical strength is 100-150Mpa.
3. prepare the method as lithium ion cell positive as claimed in claim 1 or 2, it is characterized in that: the method concrete steps are as follows:
Step 1, the preparation of High Strength Carbon Nanotubes film, utilizes carbon nano-tube macroscopic tubulose non-individual body to prepare High Strength Carbon Nanotubes film, first, at glass bar and rectangle glass surface sprinkling last layer volume fraction, is 15%-50% alcohol water blend; Then, the macroscopic view pipe non-individual body generating from reactor mouth is drawn to square glass substrate with glass bar; Adopt the form of graticules in length and breadth, that is: first along mouth of pipe direction, on glass plate, cover carbon nano-tube macroscopic pipe, obtain the rete of approximately 0.1 μ m; Then, by glass plate half-twist, before continuing, cover in the direction carbon nano-tube macroscopic pipe, obtain after the rete of approximately 0.1 μ m, again by glass plate half-twist, so repeating until obtain the High Strength Carbon Nanotubes film that thickness is 0.2-100 μ m;
Step 2 generates positive electrode material layer on carbon nano-tube rete, and positive active material, conductive agent, binding agent are mixed in proportion, with nitrogen methyl-prop pyrrolidone (NMP), regulates slurry viscosity, and solid content is controlled at 40%-50%; Ball milling 8-24h on planetary ball mill, rotating speed remains on 220-270rmin
-1above, obtain anode sizing agent; Adopt the mode of " the moving film of cutter is fixed ", the glass plate that is loaded with film is motionless, scraper is with certain edge of a knife (120-400 μ m) feed above film, by anode sizing agent " gap coating " to carbon nano-tube film, the coating of so-called gap, exactly the ink area that is coated with by necessarily not the white space of coating separate, have material region and white space alternative arrangement; Coating region lateral dimension accounts for the 0.85-0.95 of carbon nano-tube film lateral dimension, and occupy center; The required pole piece width of target battery or length that coating region longitudinal size equals 2.2 times; Coating is not reserved by lug is installed, and coating part longitudinal size is not the 1/8-3/8 of coating part longitudinal size; After coating finishes, glass plate is placed in to 100-120 ℃ of baking oven and dries, drying time is 30-60min;
Step 3, coating carbon nano-tube rete is separated with glass substrate, the glass substrate that is loaded with coating carbon nano-tube rete is kept flat, with hairbrush, dip a kind of of NMP, deionized water or alcohol, at the carbon nano-tube diaphragm area that is not coated with slurry, gently brush, after coating does not partly soak, with blade of carving knife, gently scrape the edge of carbon nano-tube film, make the edge of film separated with glass substrate, after film and glass substrate separating part area can be by clamp clamps, use fixture clamping carbon nano-tube film separating part instead, with 0.5-1cms
-1speed to not separated side, lift, until the carbon nano-tube film that scribbles slurry is separated completely from glass plate; Top scribbles the carbon nano-tube membrane portions of anodal material and can from glass plate, take off easily without sticky glutinous ground, and coating part is not dry has taken off that a little is sticky glutinous, but also can glutinous from glass substrate, take off without sticky after wetted; After end to be separated, the carbon nano-tube film that is loaded with material is put into 100-120 ℃ of baking oven and place 20-30min;
Step 4, cut-parts are also installed lug, along each not the transversal centerline in coating region film is cut into segment, use twin rollers by positive electrode material layer and carbon nano-tube film compacting, for button cell pole piece, each section need be placed on mould and go out
5-15mm disk obtains positive plate, without lug is installed; For the battery pole piece that lug need to be installed, each section further need be cut into required pole piece size in battery making, the pole piece obtaining has material part to account for 7/10-9/10, and coating does not partly account for 1/10-3/10; Because carbon nano-tube film is positioned in the middle of two aluminium foils, in two aluminium foil welding processes, carbon nano-tube film is also just firmly fixed in the middle of two aluminium foils, after fixing, aluminium foil is trimmed to required form, and the aluminium foil of wherein clamping carbon nano-tube film is lug, for making laminated battery plate, also need on aluminium foil, weld again a bit of aluminium strip with tab, the width of this section of aluminium strip equals aluminium foil width, long 1-5cm, and positive plate just completes.
4. method as claimed in claim 3, is characterized in that: in step 1, glass substrate is of a size of the m of (0.01-1.5) m * (0.01-2).
5. method as claimed in claim 3, is characterized in that: in step 2, positive active material is one or more in cobalt acid lithium, lithium nickelate, LiMn2O4, LiFePO4, lithium nickel cobalt dioxide, nickel LiMn2O4, cobalt nickel LiMn2O4.
6. method as claimed in claim 3, is characterized in that: in step 2, conductive agent is one or more in Super-P, electrically conductive graphite, Ketjen black.
7. method as claimed in claim 3, is characterized in that: in step 2, binding agent is a kind of in Kynoar, polyvinylidene fluoride, polytetrafluoroethylene, butadiene-styrene rubber.
8. method as claimed in claim 3, is characterized in that: in step 2, conductive agent quality accounts for 3%-15%, and binding agent quality accounts for 5%-10%, and all the other are positive active material.
9. method as claimed in claim 3, it is characterized in that: in step 4, the installation method of lug, when lug is positioned at pole piece side, by pole piece not coating be partly placed in the middle of two aluminium foils, aluminium foil longitudinal size be pole piece longitudinal size 1.1-1.3 doubly, thickness≤20 μ m, with pneumatic spot welding machine by upper and lower two aluminium foil seam.
10. method as claimed in claim 3, it is characterized in that: in step 4, the installation method of lug, when lug is positioned at pole piece top, with two aluminium foils pole piece 1/2 being clipped in the middle of coating parts transversely not, aluminium foil lateral dimension be not coating region lateral dimension 1/2, the 1.4-1.6 that longitudinal size is lateral dimension is doubly, thickness≤20 μ m, with pneumatic spot welding machine by upper and lower two aluminium foil seam.
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