CN101207190A - Lithium ion secondary battery anode and lithium ion secondary battery including the anode - Google Patents
Lithium ion secondary battery anode and lithium ion secondary battery including the anode Download PDFInfo
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- CN101207190A CN101207190A CNA200610170607XA CN200610170607A CN101207190A CN 101207190 A CN101207190 A CN 101207190A CN A200610170607X A CNA200610170607X A CN A200610170607XA CN 200610170607 A CN200610170607 A CN 200610170607A CN 101207190 A CN101207190 A CN 101207190A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- 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 positive electrode of a lithium ion secondary battery, which comprises a current collector and positive electrode material loaded on the current collector. The positive electrode material includes positive electrode active material, conductive agent and binding agent. The invention is characterized in that the average grain diameter D50 of the positive electrode active material is 2-10 microns, and the grain-size distribution Sigma of the positive electrode active material meets the formula; wherein, D10, D50 and D90 respectively express the corresponding average particle diameters when the accumulated grain-size distribution percent of the positive electrode active material reaches 10 percent, 50 percent and 90 percent. The positive electrode of the lithium ion secondary battery provided by the invention causes the large scaling factor discharging performance of the lithium ion secondary battery comprising the to be greatly improved; wherein, 10C/0.2C can reach as high as 88.6 percent.
Description
Technical field
The invention relates to a kind of lithium ion secondary battery positive electrode and comprise the lithium rechargeable battery that this is anodal.
Background technology
In recent years, portable power tool and electronic toy use more and more wider, receive publicity day by day as the battery of energy resource supply.What general traditional electric tool and electronic toy used is that NI-G, Ni-MH battery are the master, but day by day in the evolution of miniaturization, requires the higher secondary cell of use energy density at portable power tool and electronic toy gradually.Wherein, the development of lithium rechargeable battery is subjected to everybody growing interest.And along with the implementation of European Union's " about ban use of some harmful substance instruction in electronic electric equipment " (RoHS instruction), free of contamination lithium rechargeable battery has more the advantage of development.But, the lithium ion battery of the prior art part that also comes with some shortcomings.
What wherein, have much room for improvement most is the big multiplying power of battery, heavy-current discharge performance.Lithium rechargeable battery is in when charging, and lithium ion takes off embedding from the interlayer of the anodal oxide with layer structure that positive plate applies, and arrives negative plate by barrier film between both positive and negative polarity and electrolyte, and is embedded into the negative pole with layer structure such as the centre of material with carbon element; And the process of discharge is just in time opposite.Positive/negative plate is connected with external circuitry with lug by collector, when discharge, form loop current, deviate from from the negative pole carbon-coating in formed size of current and unit interval, be directly proportional by barrier film and electrolyte and the lithium ion number that embeds the interlayer of anodal oxide.When big multiplying power discharging, lithium ion many times when to take off the number of embedding and embedding be normal multiplying power discharging in the unit interval.As the 10C multiplying power discharging, to take off the number of embedding and embedding be 10 times of normal 1C multiplying power discharging to lithium ion in the unit interval.Under the present unmodifiable situation of lithium rechargeable battery system, a kind of effective ways that increase substantially the big multiplying power discharging property of lithium rechargeable battery are the optimal design by pole piece, as the bulk density of control positive/negative plate or the thickness of control positive/negative plate.
For example, CN 1767253A discloses a kind of lithium rechargeable battery, this battery comprises positive pole, barrier film, negative pole and nonaqueous electrolytic solution, described positive pole disengages the positive active material coating of lithium and constitutes by applying embedding on the positive electrode collector again, described negative pole disengages the negative electrode active material coating of lithium and constitutes by being coated in embedding on the negative electrode collector, wherein, the weight of described positive active material divided by the volume of positive active material coating calculate anodal coating bulk density be 1.80 gram/cubic centimetres to less than 3.50 gram/cubic centimetres, the weight of described negative electrode active material divided by the volume of negative electrode active material coating calculate the bulk density of negative pole coating be extremely less than 1.70 gram/cubic centimetres greater than 1.20 gram/cubic centimetres.This method is by reducing anodal coating bulk density and improving the big multiplying power discharging property that negative pole coating bulk density improves battery.
CN 1728440A discloses a kind of Large Ratio Lithium-Ion Rechargeable Battery, this battery comprises shell and is encapsulated in inner core body and electrolyte, described core body comprises the barrier film of positive plate, negative plate and the described positive/negative plate of isolation, comprise collector in the described positive/negative plate, the thickness of described positive plate is the 50-140 micron, and the thickness of described negative plate is the 60-150 micron.This method by reduce positive/negative plate thickness, make the amount of both positive and negative polarity active material on the unit are collector smaller, having reduced lithium ion deviates from thick from the negative plate carbon-coating, arrive the distance of positive plate by barrier film between the both positive and negative polarity and electrolyte, reduced the ionic conduction ability, strengthen the ionic conduction ability, thereby improved the big multiplying power of battery, heavy-current discharge performance.
CN 1819308A discloses a kind of lithium ion battery pole piece with high multiplying power, this pole piece comprises electrode active material, collector, adhesive and conductive agent, wherein, the thickness of described battery pole piece is between the 40-100 micron, the electrode active material of described positive pole is selected from one or both the mixture in cobalt acid lithium, the LiMn2O4, and the electrode active material of negative pole is particle diameter D
50Be distributed in the electrographite between the 5-11 micron, described adhesive is a Kynoar, described conductive agent is selected from one or both or the two or more mixtures in conductive black, superconduction carbon black, electrically conductive graphite, acetylene black, the carbon nano-tube, and the percentage by weight of electrode active material, adhesive and conductive agent is 85-96%, 2-8% and 1-10%.This method also improves the multiplying power discharging property of battery by the thickness that reduces battery pole piece, make the battery 10C multiplying power discharging time extend to 350 seconds by 10 seconds.
Said method all is the big multiplying power discharging properties that improve battery by bulk density of carrying out electrode slice or thickness, and there is no particular limitation to the kind of the The Nomenclature Composition and Structure of Complexes of battery such as negative electrode active material and positive active material and/or particle diameter.In various oxides that contain lithium that are that the particle diameter that directly is purchased is generally the 5-15 micron that are conventionally used as active material for anode of Li-ion secondary battery such as lithium cobalt oxygen, the lithium cobalt manganese one or more, because the above-mentioned oxide that contains lithium all is an insulator, certain conductive agent must be added and the conduction of electronics in positive plate could be guaranteed, conventional conductive agent is generally corpuscular electrically conductive graphite or conductive carbon black, and consumption is the 2-3 weight % of positive active material weight.Experiment showed, that above-mentioned conductive agent can't satisfy the conduction of electronics in positive plate, thereby cause battery can not obtain excellent big multiplying power discharging property.
Summary of the invention
The objective of the invention is in order to provide another kind to make battery have the lithium ion secondary battery positive electrode of good big multiplying power discharging property and to comprise the lithium rechargeable battery that this is anodal.
Lithium ion secondary battery positive electrode provided by the invention comprises collector and the positive electrode that loads on the collector, and described positive electrode contains positive active material, conductive agent and adhesive, wherein, and the average grain diameter D of described positive active material
50Be the 2-10 micron, and the particle size distribution σ of positive active material satisfies:
Lithium rechargeable battery provided by the invention comprises battery container, pole piece and electrolyte, described pole piece and electrolyte are sealed in the battery container, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, wherein, described lithium ion secondary battery positive electrode just very provided by the invention.
Lithium ion secondary battery positive electrode provided by the invention is by the particle diameter and the granularity of control positive active material, make and comprise that the big multiplying power discharging property of the lithium rechargeable battery that this is anodal improves greatly, for example, it is 99.0% that the multiplying power discharging property of the lithium rechargeable battery that is made by the embodiment of the invention 3 is respectively 3C/0.2C, 5C/0.2C be 94.1%, 10C/0.2C be 88.6%, and adopt battery that prior art makes because of using the lithium cobalt oxygen that directly is commercially available and native graphite as positive active material and negative electrode active material, thereby the multiplying power discharging property under other condition same case is 83.2% for 3C/0.2C only, 5C/0.2C be 57.2%, 10C/0.2C is 7.9%.
In addition, according to one embodiment of the present invention, when using carbon nano-tube as positive pole and/or cathode conductive agent, carbon nano-tube has higher conductivity on the one hand, can improve the conductivity of both positive and negative polarity; Carbon nano-tube can guarantee at the inner favorable conductive network that forms of positive plate on the other hand, solved the conductor defect of insufficient that might exist, further improved the big multiplying power discharging property of lithium rechargeable battery because granular pattern electric conducting material such as electrically conductive graphite finish electric action by a contact.
Embodiment
According to positive pole provided by the invention, the average grain diameter D of wherein said positive active material
50Be preferably the 3-8 micron.If D
50Greater than 10 microns, then can not obtain well big multiplying power discharging property.If D
50Less than 2 microns, then, increase the reaction between positive active material and the electrolyte, make the high-temperature stability of battery descend because the too for a short time specific surface that causes of the particle diameter of positive active material increases, and battery can be emitted a large amount of heat when big multiplying power discharging, therefore can cause the high rate performance of battery to descend.If the particle of positive active material is little simultaneously, specific surface is big, needs relatively large adhesive could guarantee that positive active material is attached on the plus plate current-collecting body.The increase of amount of binder reduces the capacity of battery on the one hand, also can reduce the multiplying power discharging property of battery on the other hand.According to the present invention, if the distribution of positive active material particle diameter
Greater than 4, then because the positive active material granular size differs bigger, the speed that lithium ion embeds between positive electrode active material layer in the guiding discharge process differs bigger, reduces big multiplying power discharging property.D wherein
10, D
50, D
90Continue to use the implication of this area routine respectively, the cumulative particle sizes percentile of promptly representing the positive active material particle respectively reaches 10%, 50% and 90% o'clock pairing mean particle diameter.
Described positive active material can be the positive active material of the embedded removal lithium embedded of this area routine, as in the stratiform lithium composite xoide of available following chemical formulation lithium and transition metal one or more: Li
xNi
1-yCo
yO
2(wherein, 0.9≤x≤1.1,0≤y≤1), Li
xMn
2-yB
yO
2(wherein, B is a transition metal or nonmetal, 0.9≤x≤1.1,0≤y≤1) is preferably lithium cobalt oxygen (LiCoO
2).
Described conductive agent can be the conventional anodal conductive agent that uses in this area, as in acetylene black, electrically conductive graphite, conductive black, carbon nano-tube and various metallic such as the copper one or more.The inventor is surprised to find that, use and contain diameter and be the 1-100 nanometer, be preferably the 10-50 nanometer, draw ratio is more than or equal to 100 conductive agents as the carbon nano-tube of 100-10000, not only can in positive active material, form good electron conduction network, solved the conductor defect of insufficient that might exist because granular pattern electric conducting material such as electrically conductive graphite finish electric action by a contact, further improved the big multiplying power discharging property of lithium rechargeable battery, and the dispersiveness in water is better, when the preparation anode sizing agent, be not easy to reunite, also has imbibition ability preferably in addition, lower resistivity.Carbon nano-tube with above-mentioned size can be commercially available, and also can obtain by the prepared in various methods of prior art.Total amount with conductive agent is a benchmark, and the content of described carbon nano-tube can be 20-90 weight %, is preferably 30-80 weight %; The content of other conductive agent can be 10-80 weight %, is preferably 20-70 weight %.
Described adhesive can be a various adhesive of the prior art, as polytetrafluoroethylene adhesive, polyvinylidene fluoride (PVDF) adhesive.Among the present invention, in order further to improve the dissolubility of adhesive in water, under the preferable case, be benchmark with the total amount of adhesive, the content of described enol based polyalcohol is 20-100 weight %, is preferably 50-90 weight %.Described enol based polyalcohol can be various water soluble alkene alcohol based polyalcohols, for example can be in polyvinyl alcohol, POLYPROPYLENE GLYCOL, the polyisobutene alcohol one or more.Because the dissolubility of polyvinyl alcohol in water be good, have good adhesive property, therefore preferred described enol based polyalcohol is a polyvinyl alcohol.
Owing to have active group among conventional adhesive such as the PVDF, under the strong oxidation environment of lithium ion cell positive, too much active group easily and other material such as electrolyte reacts or self decomposes in traditional adhesive, causes battery can't normally give play to capacity.And the active group that is used in the enol based polyalcohol of positive electrode of the present invention is less, eliminated the influence of active group, avoided because the loss of the battery capacity that adhesive causes, hydroxyl in the enol based polyalcohol has binding ability preferably with the decomposition group of the water that forms in the metal surface simultaneously, can guarantee adhesive property good between positive active material and the metal collector, therefore active material is unlikely and comes off in charge and discharge cycles repeatedly, has guaranteed the cycle performance and the high-rate discharge ability of battery.And during lithium ion battery anode glue size, used solvent is a water in preparation, and the temperature requirement of solvent evaporation when having reduced film-making makes more convenient operation.
The degree of polymerization of enol based polyalcohol has determined the viscosity (also being caking property) of this polymer, and viscosity is directly proportional with the degree of polymerization.If the degree of polymerization is too small, then the adhesive property variation of polymer causes the cycle performance of battery relatively poor; The degree of polymerization is excessive, and then viscosity is too big, and positive electrode is difficult to be coated on the collector body equably.Therefore, though higher or be available than the enol based polyalcohol of low polymerization degree, under the preferable case, the degree of polymerization of enol based polyalcohol is 1700-5000, is preferably 1900-3000.
The alcoholysis degree of enol based polyalcohol also is the factor that influences this polymer viscosity, the alcoholysis degree of described enol based polyalcohol is meant polyvinyl acetate is being carried out alcoholysis, just polyvinyl acetate is reduced and obtain in the process of polyvinyl alcohol, the degree of polyvinyl acetate reduction (alcoholysis), alcoholysis degree is high more, and it is high more to represent that then polyvinyl acetate is reduced into the degree of polyvinyl alcohol.As the alcoholysis degree of pectin/polyvinyl alcohol less than 70%, the decreased solubility of polymer in water then, alcoholysis degree is water insoluble substantially less than 65% polyvinyl alcohol; And alcoholysis degree can only be dissolved in the water more than 95 ℃ greater than 99% polyvinyl alcohol, and its bad stability in water.The product of alcoholysis degree 80-95% is water-soluble best, and this helps to form netted stable structure in water, makes the maximum effect of adhesive property performance to guarantee that simultaneously positive active material is uniformly dispersed.Though higher or be available than the enol based polyalcohol of low alcoholysis level, under the preferable case, the alcoholysis degree of the based polyalcohol of enol described in the present invention is preferably 80-95% at 70-99%.
According to a specific embodiment of the present invention, in order better to guarantee the utilance of positive active material, make between the positive active material particle, reach the even distribution between positive active material and the electrolyte between positive active material and the conductive agent particle, under the preferable case, described adhesive also contains as the slaine of the cellulose-based polymer of thickener and/or cellulose-based polymer to increase the viscosity of positive electrode, and described cellulose-based polymer is selected from carboxymethyl cellulose (CMC), methylcellulose, ethyl cellulose, hydroxypropyl methylcellulose (HPMC), in the Hydroxypropyl ethyl cellulose one or more.In order to increase the solubility of cellulose-based polymer in water, the slaine of described cellulose-based polymer is selected from the sodium salt or the ammonium salt of cellulose-based polymer.
Has higher ionic conductivity as the cellulose-based polymer of thickener or the sodium salt or the ammonium salt of cellulose-based polymer, when the enol based polyalcohol being mixed use preparation anode sizing agent with cellulose-based polymer, can be dispersed in the whole slurry with molecular level, form in can the anode pole piece after coating between between the positive active material particle, between positive active material and the conductive agent particle and and electrolyte between uniform thin layer, strengthen the ionic conductivity between solid-liquid, therefore improved the discharge performance of battery.
The content of positive active material, conductive agent and adhesive can be the corresponding content of each component in the conventional positive electrode in the described positive electrode, for example, total amount with positive electrode is a benchmark, the content of positive active material can be 85-98.5 weight %, be preferably 94-98 weight %, the content of conductive agent can be 0.5-10 weight %, is preferably 1-3 weight %, the content of adhesive can be 0.5-5 weight %, is preferably 1-3 weight %.
The present invention is not particularly limited forming anodal collector body, can be positive electrode collector conventional in the lithium ion battery, uses aluminium foil as positive electrode collector in specific embodiments of the present invention.
Lithium ion cell positive provided by the invention can obtain by prepared in various methods, for example can apply by the slurry that will contain positive active material, conductive agent and adhesive and solvent and/or be filled on the collector body, dry, pressing mold or do not obtain behind the pressing mold, the described slurry that contains positive active material, conductive agent and adhesive and solvent can by earlier with positive active material and conductive agent dry powder blend evenly after, mix and obtain with adhesive, solvent or adhesive binder solution again with solvent formation; It is even with positive active material, adhesive and solvent also can to pass through elder generation, and then mixes with conductive agent, obtains slurry.Owing to contain water miscible enol based polyalcohol in the adhesive and conductive agent can not reunited in water, therefore, described solvent is preferably water.The consumption of solvent can make described pastel have viscosity and flowability, can be coated on the described collector body to get final product.Method and condition dry, pressing mold are conventionally known to one of skill in the art.
According to lithium rechargeable battery provided by the invention, described negative pole, barrier film and nonaqueous electrolytic solution can be conventional negative pole, barrier film, the nonaqueous electrolytic solution that uses in this area.
For example, described negative pole comprises collector body and coating and/or is filled in negative material on the collector body that described negative material comprises negative electrode active material and adhesive.
Described negative electrode active material is not particularly limited, can use embedding of this area routine to disengage the negative electrode active material of lithium, such as in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal, the silicon alloy one or more, preferred electrographite.
Although the negative electrode active material of conventional particle diameter and particle size distribution can be realized purpose of the present invention, under the preferable case, in order further to improve the big multiplying power discharging of battery, the average grain diameter D of described negative electrode active material
50Be the 5-15 micron, be preferably the 12-15 micron, and the particle size distribution σ of negative electrode active material satisfies
Described negative material can also comprise conductive agent, described conductive agent is not particularly limited, can be the cathode conductive agent of this area routine, such as in ketjen carbon black, acetylene black, furnace black, carbon fiber VGCF, conductive carbon black, carbon nano-tube and the electrically conductive graphite one or more.
The inventor finds, use contain diameter as the 1-100 nanometer, be preferably the 10-50 nanometer, draw ratio can further improve the big multiplying power discharging of battery more than or equal to 100 conductive agents as the carbon nano-tube of 100-10000.Total amount with conductive agent is a benchmark, and the content of described carbon nano-tube can be 20-90 weight %, is preferably 30-80 weight %; The content of other conductive agent can be 10-80 weight %, is preferably 20-70 weight %.
The kind of described adhesive and content are conventionally known to one of skill in the art, for example one or more in fluorine resin and polyolefin compound such as Kynoar (PVDF), polytetrafluoroethylene (PTFE), the butadiene-styrene rubber (SBR).
Under the preferable case, described negative pole adhesive adopts the mixture of cellulose-based polymer and rubber latex, as the mixture of cellulose-based polymer and butadiene-styrene rubber (SBR).The consumption of described cellulose-based polymer and butadiene-styrene rubber is conventionally known to one of skill in the art.
The content of negative electrode active material, conductive agent and adhesive can be the corresponding content of each component in the conventional negative material in the described negative material, for example, total amount with negative material is a benchmark, the content of negative electrode active material can be 85-99.4 weight %, be preferably 92-98.8 weight %, the content of conductive agent can be 0.5-10 weight %, is preferably 1-3 weight %, the content of adhesive can be 0.1-8 weight %, is preferably 0.2-5 weight %.
Negative electrode collector can be for negative electrode collector conventional in the lithium ion battery, as stamped metal, and metal forming, net metal, foamed metal uses Copper Foil as negative electrode collector in specific embodiments of the present invention.
Described barrier film can be selected from various barrier films used in the lithium ion battery, as the high molecular polymer microporous membrane, comprises polypropylene microporous film and polypropylene and poly MULTILAYER COMPOSITE microporous membrane.The position of described barrier film, character and kind are conventionally known to one of skill in the art.
Described nonaqueous electrolytic solution is the mixed solution of electrolyte lithium salt and nonaqueous solvents, and it is not particularly limited, and can use the nonaqueous electrolytic solution of this area routine.Be selected from lithium hexafluoro phosphate (LiPF such as electrolyte lithium salt
6), in lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and the fluorocarbon based sulfonic acid lithium one or more.Organic solvent is selected chain acid esters and ring-type acid esters mixed solution for use, wherein the chain acid esters can be dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other are fluorine-containing, sulfur-bearing or contain at least a in the chain organosilane ester of unsaturated bond, the ring-type acid esters can be ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton (γ-BL), sultone and other are fluorine-containing, sulfur-bearing or contain at least a in the ring-type organosilane ester of unsaturated bond.The injection rate of electrolyte is generally 1.5-4.9 gram/ampere-hour, and the concentration of electrolyte is generally the 0.5-2.9 mol.
The following examples will the present invention is described further.Since between different positive active materials or the same a kind of positive active material produced by different manufacturers and the big multiplying power discharging property between different negative electrode active material or the same a kind of negative electrode active material produced by different manufacturers exist than big-difference, therefore, for embodying advantage of the present invention, following embodiment and Comparative Examples all adopt same batch the lithium cobalt oxygen (FMC commodity) of same model of same manufacturer production as positive active material, (the soddif commodity are DAG22) as negative electrode active material to adopt same batch the native graphite of same model of same manufacturer production.By positive active material and negative electrode active material that the method that adopts the screen cloth in different apertures to sieve to positive active material and negative electrode active material respectively obtains having different-grain diameter and particle size distribution, the result is as shown in table 1, wherein is numbered the LiCoO of Z5 in the table 1
2With the commodity of the native graphite that is numbered F5 for directly being commercially available.
Table 1
Embodiment 1
This embodiment is used to illustrate lithium ion secondary battery positive electrode of the present invention and contains this anodal lithium rechargeable battery.
Get the LiCoO that is numbered Z3 on 100 weight portions in the table 1
2(diameter is the 10-40 nanometer to the carbon nano-tube of powder, 1 weight portion, draw ratio is 500, Taiwan remittance company of heap of stone commodity), 2 weight portion electrically conductive graphite KS6 (TIMICAL company product) and 3 parts by weight of polyvinylidene fluoride (PVDF) are fully mixed, be dissolved in 200 milliliters of N-methyl pyrrolidones, form uniform pastel.This pasty state is coated to the two sides that thickness is 20 microns aluminium foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 540 millimeters, wide 43.5 millimeters positive plate.Positive electrode content on this positive plate is 3.6 grams.
Get the native graphite that is numbered F1 on 100 weight portions in the table 1 and fully mix, be dissolved in 200 milliliters the N-methyl pyrrolidone, form uniform pastel with 4 parts by weight of polyvinylidene fluoride (PVDF).This pasty state is coated to the two sides that thickness is 12 microns Copper Foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 500 millimeters, wide 44 millimeters negative plate.Negative material content on this negative plate is 1.7 grams.
Above-mentioned positive and negative plate and polypropylene screen are wound into the pole piece of square lithium ion battery, subsequently with LiPF
6Concentration by 1 mol is dissolved in ethylene carbonate: the Methylethyl carbonic ester: diethyl carbonate (EC/EMC/DEC) volume ratio is to form nonaqueous electrolytic solution in 1: 1: 1 the mixed solvent, this electrolyte is injected battery container with the amount of 3.8 gram/ampere-hours, seal, make the lithium ion battery A1 of LP043450A type.
Embodiment 2
This embodiment is used to illustrate lithium ion secondary battery positive electrode of the present invention and contains this anodal lithium rechargeable battery.
Get the LiCoO that is numbered Z3 on 100 weight portions in the table 1
2(diameter is the 50-140 nanometer to the carbon nano-tube of powder, 1 weight portion, draw ratio is 500, Taiwan remittance company of heap of stone commodity), 3 weight portion electrically conductive graphite KS6 (TIMICAL company product) and 3 parts by weight of polyvinylidene fluoride (PVDF) are fully mixed, be dissolved in 200 milliliters of N-methyl pyrrolidones, form uniform pastel.This pasty state is coated to the two sides that thickness is 20 microns aluminium foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 540 millimeters, wide 43.5 millimeters positive plate.Positive electrode content on this positive plate is 3.6 grams.
Get the native graphite that is numbered F3 on 100 weight portions in the table 1 and fully mix, be dissolved in 200 milliliters the N-methyl pyrrolidone, form uniform pastel with 4 parts by weight of polyvinylidene fluoride (PVDF).This pasty state is coated to the two sides that thickness is 12 microns Copper Foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 500 millimeters, wide 44 millimeters negative plate.Negative material content on this negative plate is 1.7 grams.
Above-mentioned positive and negative plate and polypropylene screen are wound into the pole piece of square lithium ion battery, subsequently with LiPF
6Concentration by 1 mol is dissolved in ethylene carbonate: the Methylethyl carbonic ester: diethyl carbonate (EC/EMC/DEC) volume ratio is to form nonaqueous electrolytic solution in 1: 1: 1 the mixed solvent, this electrolyte is injected battery container with the amount of 3.8 gram/ampere-hours, seal, make the lithium ion battery A2 of LP043450A type.
Embodiment 3
This embodiment is used to illustrate lithium ion secondary battery positive electrode of the present invention and contains this anodal lithium rechargeable battery.
Get the LiCoO that is numbered Z1 on 100 weight portions in the table 1
2(diameter is the 10-40 nanometer to the carbon nano-tube of powder, 3 weight portions, draw ratio is 500, Taiwan remittance company of heap of stone commodity), (degree of polymerization is 1900 for the 2 weight portion electrically conductive graphite KS6 (TIMICAL company product) and the polyvinyl alcohol of 3 weight portions, alcoholysis degree is 80%) in 100 weight parts waters, fully mix, form uniform pastel.This pasty state is coated to the two sides that thickness is 20 microns aluminium foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 540 millimeters, wide 43.5 millimeters positive plate.Positive electrode content on this positive plate is 3.6 grams.
Get the native graphite that is numbered F1 on 100 weight portions in the table 1, (diameter is the 10-40 nanometer to the carbon nano-tube of 3 weight portions, draw ratio is 500, Taiwan remittance company of heap of stone commodity), 2 weight portion electrically conductive graphite KS6 (TIMICAL company product) fully mix with 4 parts by weight of polyvinylidene fluoride (PVDF), be dissolved in 200 milliliters the N-methyl pyrrolidone, form uniform pastel.This pasty state is coated to the two sides that thickness is 12 microns Copper Foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 500 millimeters, wide 44 millimeters negative plate.Negative material content on this negative plate is 1.7 grams.
Above-mentioned positive and negative plate and polypropylene screen are wound into the pole piece of square lithium ion battery, subsequently with LiPF
6Concentration by 1 mol is dissolved in ethylene carbonate: the Methylethyl carbonic ester: diethyl carbonate (EC/EMC/DEC) volume ratio is to form nonaqueous electrolytic solution in 1: 1: 1 the mixed solvent, this electrolyte is injected battery container with the amount of 3.8 gram/ampere-hours, seal, make the lithium ion battery A3 of LP043450A type.
Embodiment 4
This embodiment is used to illustrate lithium ion secondary battery positive electrode of the present invention and contains this anodal lithium rechargeable battery.
Get the LiCoO that is numbered Z1 on 100 weight portions in the table 1
2Carbon nano-tube of powder, 1.5 weight portions (diameter is the 10-40 nanometer, and draw ratio is 500, and company of heap of stone commodity converge in Taiwan) and 3 parts by weight of polyvinylidene fluoride (PVDF) are fully mixed, and are dissolved in 200 milliliters of N-methyl pyrrolidones, form uniform pastel.This pasty state is coated to the two sides that thickness is 20 microns aluminium foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 540 millimeters, wide 43.5 millimeters positive plate.Positive electrode content on this positive plate is 3.6 grams.
Get the native graphite that is numbered F3 on 100 weight portions in the table 1 and fully mix, be dissolved in 200 milliliters the N-methyl pyrrolidone, form uniform pastel with 4 parts by weight of polyvinylidene fluoride (PVDF).This pasty state is coated to the two sides that thickness is 12 microns Copper Foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 500 millimeters, wide 44 millimeters negative plate.Negative material content on this negative plate is 1.7 grams.
Above-mentioned positive and negative plate and polypropylene screen are wound into the pole piece of square lithium ion battery, subsequently with LiPF
6Concentration by 1 mol is dissolved in ethylene carbonate: the Methylethyl carbonic ester: diethyl carbonate (EC/EMC/DEC) volume ratio is to form nonaqueous electrolytic solution in 1: 1: 1 the mixed solvent, this electrolyte is injected battery container with the amount of 3.8 gram/ampere-hours, seal, make the lithium ion battery A4 of LP043450A type.
Embodiment 5
This embodiment is used to illustrate lithium ion secondary battery positive electrode of the present invention and contains this anodal lithium rechargeable battery.
Get the LiCoO that is numbered Z2 on 100 weight portions in the table 1
2(diameter is the 10-40 nanometer to the carbon nano-tube of powder, 1.5 weight portions, draw ratio is 500, Taiwan remittance company of heap of stone commodity), 2 weight portion electrically conductive graphite KS6 (TIMICAL company product) and 3 parts by weight of polyvinylidene fluoride (PVDF) are fully mixed, be dissolved in 200 milliliters of N-methyl pyrrolidones, form uniform pastel.This pasty state is coated to the two sides that thickness is 20 microns aluminium foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 540 millimeters, wide 43.5 millimeters positive plate.Positive electrode content on this positive plate is 3.6 grams.
Get the native graphite that is numbered F2 on 100 weight portions in the table 1, (diameter is the 10-40 nanometer to the carbon nano-tube of 3 weight portions, draw ratio is 500, Taiwan remittance company of heap of stone commodity), 2 weight portion electrically conductive graphite KS6 (TIMICAL company product) fully mix with 4 parts by weight of polyvinylidene fluoride (PVDF), be dissolved in 200 milliliters the N-methyl pyrrolidone, form uniform pastel.This pasty state is coated to the two sides that thickness is 12 microns Copper Foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 500 millimeters, wide 44 millimeters negative plate.Negative material content on this negative plate is 1.7 grams.
Above-mentioned positive and negative plate and polypropylene screen are wound into the pole piece of square lithium ion battery, subsequently with LiPF
6Concentration by 1 mol is dissolved in ethylene carbonate: the Methylethyl carbonic ester: diethyl carbonate (EC/EMC/DEC) volume ratio is to form nonaqueous electrolytic solution in 1: 1: 1 the mixed solvent, this electrolyte is injected battery container with the amount of 3.8 gram/ampere-hours, seal, make the lithium ion battery A5 of LP043450A type.
Embodiment 6
This embodiment is used to illustrate lithium ion secondary battery positive electrode of the present invention and contains this anodal lithium rechargeable battery.
Get the LiCoO that is numbered Z2 on 100 weight portions in the table 1
2Powder, 3 weight portion electrically conductive graphite KS6 (TIMICAL company product) and 3 parts by weight of polyvinylidene fluoride (PVDF) are fully mixed, and are dissolved in 200 milliliters of N-methyl pyrrolidones, form uniform pastel.This pasty state is coated to the two sides that thickness is 20 microns aluminium foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 540 millimeters, wide 43.5 millimeters positive plate.Positive electrode content on this positive plate is 3.6 grams.
Get the native graphite that is numbered F4 on 100 weight portions in the table 1 and fully mix, be dissolved in 200 milliliters the N-methyl pyrrolidone, form uniform pastel with 4 parts by weight of polyvinylidene fluoride (PVDF).This pasty state is coated to the two sides that thickness is 12 microns Copper Foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 500 millimeters, wide 44 millimeters negative plate.Negative material content on this negative plate is 1.7 grams.
Above-mentioned positive and negative plate and polypropylene screen are wound into the pole piece of square lithium ion battery, subsequently with LiPF
6Concentration by 1 mol is dissolved in ethylene carbonate: the Methylethyl carbonic ester: diethyl carbonate (EC/EMC/DEC) volume ratio is to form nonaqueous electrolytic solution in 1: 1: 1 the mixed solvent, this electrolyte is injected battery container with the amount of 3.8 gram/ampere-hours, seal, make the lithium ion battery A6 of LP043450A type.
Embodiment 7
This embodiment is used to illustrate lithium ion secondary battery positive electrode of the present invention and contains this anodal lithium rechargeable battery.
Get the LiCoO that is numbered Z2 on 100 weight portions in the table 1
2Powder, 3 weight portion electrically conductive graphite KS6 (TIMICAL company product) and 3 parts by weight of polyvinylidene fluoride (PVDF) are fully mixed, and are dissolved in 200 milliliters of N-methyl pyrrolidones, form uniform pastel.This pasty state is coated to the two sides that thickness is 20 microns aluminium foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 540 millimeters, wide 43.5 millimeters positive plate.Positive electrode content on this positive plate is 3.6 grams.
Get the native graphite that is numbered F5 on 100 weight portions in the table 1 and fully mix, be dissolved in 200 milliliters the N-methyl pyrrolidone, form uniform pastel with 4 parts by weight of polyvinylidene fluoride (PVDF).This pasty state is coated to the two sides that thickness is 12 microns Copper Foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 500 millimeters, wide 44 millimeters negative plate.Negative material content on this negative plate is 1.7 grams.
Above-mentioned positive and negative plate and polypropylene screen are wound into the pole piece of square lithium ion battery, subsequently with LiPF
6Concentration by 1 mol is dissolved in ethylene carbonate: the Methylethyl carbonic ester: diethyl carbonate (EC/EMC/DEC) volume ratio is to form nonaqueous electrolytic solution in 1: 1: 1 the mixed solvent, this electrolyte is injected battery container with the amount of 3.8 gram/ampere-hours, seal, make the lithium ion battery A7 of LP043450A type.
Comparative Examples 1
This Comparative Examples is used to illustrate existing lithium ion secondary battery positive electrode and contains this anodal lithium rechargeable battery.
Get the LiCoO that is numbered Z4 on 100 weight portions in the table 1
2(diameter is the 10-40 nanometer to the carbon nano-tube of powder, 3 weight portions, draw ratio is 500, Taiwan remittance company of heap of stone commodity), (degree of polymerization is 1900 for the 2 weight portion electrically conductive graphite KS6 (TIMICAL company product) and the polyvinyl alcohol of 3 weight portions, alcoholysis degree is 80%) in 100 weight parts waters, fully mix, form uniform pastel.This pasty state is coated to the two sides that thickness is 20 microns aluminium foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 540 millimeters, wide 43.5 millimeters positive plate.Positive electrode content on this positive plate is 3.6 grams.
Get the native graphite that is numbered F4 on 100 weight portions in the table 1, (diameter is the 10-40 nanometer to the carbon nano-tube of 3 weight portions, draw ratio is 500, Taiwan remittance company of heap of stone commodity), 2 weight portion electrically conductive graphite KS6 (TIMICAL company product) fully mix with 4 parts by weight of polyvinylidene fluoride (PVDF), be dissolved in 200 milliliters the N-methyl pyrrolidone, form uniform pastel.This pasty state is coated to the two sides that thickness is 12 microns Copper Foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 500 millimeters, wide 44 millimeters negative plate.Negative material content on this negative plate is 1.7 grams.
Above-mentioned positive and negative plate and polypropylene screen are wound into the pole piece of square lithium ion battery, subsequently with LiPF
6Concentration by 1 mol is dissolved in ethylene carbonate: the Methylethyl carbonic ester: diethyl carbonate (EC/EMC/DEC) volume ratio is to form nonaqueous electrolytic solution in 1: 1: 1 the mixed solvent, this electrolyte is injected battery container with the amount of 3.8 gram/ampere-hours, seal, make the reference lithium ion battery CA1 of LP043450A type.
Comparative Examples 2
This Comparative Examples is used to illustrate existing lithium ion secondary battery positive electrode and contains this anodal lithium rechargeable battery.
Get the LiCoO that is numbered Z4 on 100 weight portions in the table 1
2(diameter is the 10-40 nanometer to the carbon nano-tube of powder, 3 weight portions, draw ratio is 500, Taiwan remittance company of heap of stone commodity), (degree of polymerization is 1900 for the 2 weight portion electrically conductive graphite KS6 (TIMICAL company product) and the polyvinyl alcohol of 3 weight portions, alcoholysis degree is 80%) in 100 weight parts waters, fully mix, form uniform pastel.This pasty state is coated to the two sides that thickness is 20 microns aluminium foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 540 millimeters, wide 43.5 millimeters positive plate.Positive electrode content on this positive plate is 3.6 grams.
Get the native graphite that is numbered F1 on 100 weight portions in the table 1, (diameter is the 10-40 nanometer to the carbon nano-tube of 3 weight portions, draw ratio is 500, Taiwan remittance company of heap of stone commodity), 2 weight portion electrically conductive graphite KS6 (TIMICAL company product) fully mix with 4 parts by weight of polyvinylidene fluoride (PVDF), be dissolved in 200 milliliters the N-methyl pyrrolidone, form uniform pastel.This pasty state is coated to the two sides that thickness is 12 microns Copper Foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 500 millimeters, wide 44 millimeters negative plate.Negative material content on this negative plate is 1.7 grams.
Above-mentioned positive and negative plate and polypropylene screen are wound into the pole piece of square lithium ion battery, subsequently with LiPF
6Concentration by 1 mol is dissolved in ethylene carbonate: the Methylethyl carbonic ester: diethyl carbonate (EC/EMC/DEC) volume ratio is to form nonaqueous electrolytic solution in 1: 1: 1 the mixed solvent, this electrolyte is injected battery container with the amount of 3.8 gram/ampere-hours, seal, make the reference lithium ion battery CA2 of LP043450A type.
Comparative Examples 3
This Comparative Examples is used to illustrate existing lithium ion secondary battery positive electrode and contains this anodal lithium rechargeable battery.
Get the LiCoO that is numbered Z5 on 100 weight portions in the table 1
2(diameter is the 10-40 nanometer to the carbon nano-tube of powder, 3 weight portions, draw ratio is 500, Taiwan remittance company of heap of stone commodity), (degree of polymerization is 1900 for the 2 weight portion electrically conductive graphite KS6 (TIMICAL company product) and the polyvinyl alcohol of 3 weight portions, alcoholysis degree is 80%) in 100 weight parts waters, fully mix, form uniform pastel.This pasty state is coated to the two sides that thickness is 20 microns aluminium foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 540 millimeters, wide 43.5 millimeters positive plate.Positive electrode content on this positive plate is 3.6 grams.
Get the native graphite that is numbered F1 on 100 weight portions in the table 1, (diameter is the 10-40 nanometer to the carbon nano-tube of 3 weight portions, draw ratio is 500, Taiwan remittance company of heap of stone commodity), 2 weight portion electrically conductive graphite KS6 (TIMICAL company product) fully mix with 4 parts by weight of polyvinylidene fluoride (PVDF), be dissolved in 200 milliliters the N-methyl pyrrolidone, form uniform pastel.This pasty state is coated to the two sides that thickness is 12 microns Copper Foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 500 millimeters, wide 44 millimeters negative plate.Negative material content on this negative plate is 1.7 grams.
Above-mentioned positive and negative plate and polypropylene screen are wound into the pole piece of square lithium ion battery, subsequently with LiPF
6Concentration by 1 mol is dissolved in ethylene carbonate: the Methylethyl carbonic ester: diethyl carbonate (EC/EMC/DEC) volume ratio is to form nonaqueous electrolytic solution in 1: 1: 1 the mixed solvent, this electrolyte is injected battery container with the amount of 3.8 gram/ampere-hours, seal, make the reference lithium ion battery CA3 of LP043450A type.
Comparative Examples 4
This Comparative Examples is used to illustrate existing lithium ion secondary battery positive electrode and contains this anodal lithium rechargeable battery.
Get the LiCoO that is numbered Z5 on 100 weight portions in the table 1
2(diameter is the 10-40 nanometer to the carbon nano-tube of powder, 3 weight portions, draw ratio is 500, Taiwan remittance company of heap of stone commodity), (degree of polymerization is 1900 for the 2 weight portion electrically conductive graphite KS6 (TIMICAL company product) and the polyvinyl alcohol of 3 weight portions, alcoholysis degree is 80%) in 100 weight parts waters, fully mix, form uniform pastel.This pasty state is coated to the two sides that thickness is 20 microns aluminium foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 540 millimeters, wide 43.5 millimeters positive plate.Positive electrode content on this positive plate is 3.6 grams.
Get the native graphite that is numbered F5 on 100 weight portions in the table 1, (diameter is the 10-40 nanometer to the carbon nano-tube of 3 weight portions, draw ratio is 500, Taiwan remittance company of heap of stone commodity), 2 weight portion electrically conductive graphite KS6 (TIMICAL company product) fully mix with 4 parts by weight of polyvinylidene fluoride (PVDF), be dissolved in 200 milliliters the N-methyl pyrrolidone, form uniform pastel.This pasty state is coated to the two sides that thickness is 12 microns Copper Foil equably, 150 ℃ of following oven dry, roll-ins afterwards, cuts and make long 500 millimeters, wide 44 millimeters negative plate.Negative material content on this negative plate is 1.7 grams.
Above-mentioned positive and negative plate and polypropylene screen are wound into the pole piece of square lithium ion battery, subsequently with LiPF
6Concentration by 1 mol is dissolved in ethylene carbonate: the Methylethyl carbonic ester: diethyl carbonate (EC/EMC/DEC) volume ratio is to form nonaqueous electrolytic solution in 1: 1: 1 the mixed solvent, this electrolyte is injected battery container with the amount of 3.8 gram/ampere-hours, seal, make the reference lithium ion battery CA4 of LP043450A type.
Embodiment 8-14
Following embodiment is used to illustrate the big multiplying power discharging property of lithium rechargeable battery of the present invention.
Respectively the lithium rechargeable battery A1-A7 that is made by embodiment 1-7 is carried out big multiplying power discharging test according to following method, the result is as shown in table 2:
Lithium ion battery A1, A2, A3, A4, A5, A6 and the A7 that will be made by the foregoing description 1-7 is respectively after storing 48 hours under 45 ℃ the environment, at room temperature, seal after 6 hours with the current charges of 0.1C more earlier with the current charges of 0.05C (design 1C is 500 MAHs) 4 hours.With the current discharge of battery with 1C, discharge is by 3.0 volts of voltages after having sealed.Again with the electric current of 0.5C to battery charge, charging is by 3.85 volts of voltages, finish the activation of battery thus, then above-mentioned battery is measured 0.2C, 3C, 5C and the 10C discharge capacity of each battery and the ratio of calculating and 0.2C discharge capacity respectively according to following method, obtains 3C/0.2C, 5C/0.2C and 10C/0.2C multiplying power discharging property:
0.2C discharge capacity: under 23 ℃ of conditions, above-mentioned battery respectively with 1C current charges to 4.2 volt, is risen to 4.2 volts of backs with constant-potential charge at voltage, cut-off current is 0.05C, shelves 10 minutes; With 0.2C current discharge to 3.0 volt, write down the discharge capacity of 0.2C electric current then;
The 3C discharge capacity: under 23 ℃ of conditions, above-mentioned battery respectively with 1C current charges to 4.2 volt, is risen to 4.2 volts of backs with constant-potential charge at voltage, cut-off current is 0.05C, shelves 10 minutes; With 3C current discharge to 3.0 volt, write down the discharge capacity of 3C electric current then;
The 5C discharge capacity: under 23 ℃ of conditions, above-mentioned battery respectively with 1C current charges to 4.2 volt, is risen to 4.2 volts of backs with constant-potential charge at voltage, cut-off current is 0.05C, shelves 10 minutes; With 5C current discharge to 3.0 volt, write down the discharge capacity of 5C electric current then;
The 10C discharge capacity: under 23 ℃ of conditions, above-mentioned battery respectively with 1C current charges to 4.2 volt, is risen to 4.2 volts of backs with constant-potential charge at voltage, cut-off current is 0.05C, shelves 10 minutes; With 10C current discharge to 3.0 volt, write down the discharge capacity of 10C electric current then.
Comparative Examples 5-8
According to the described method of embodiment 8-14 the reference lithium rechargeable battery CA1-CA4 that is made by Comparative Examples 1-4 is carried out big multiplying power discharging property test, the result is as shown in table 2.
Table 2
From the result of last table 2 as can be seen, lithium rechargeable battery provided by the invention has excellent big multiplying power discharging property.
Claims (10)
1. lithium ion secondary battery positive electrode, this positive pole comprise collector and load on positive electrode on the collector that described positive electrode contains positive active material, conductive agent and adhesive, it is characterized in that the average grain diameter D of described positive active material
50Be the 2-10 micron, and the particle size distribution σ of positive active material satisfies:
Wherein, D
10, D
50, D
90The cumulative particle sizes percentile of representing the positive active material particle respectively reaches 10%, 50% and 90% o'clock pairing mean particle diameter.
2. lithium ion secondary battery positive electrode according to claim 1, wherein, described conductive agent contains carbon nano-tube.
3. lithium ion secondary battery positive electrode according to claim 2 wherein, is a benchmark with the total amount of conductive agent, and the content of described carbon nano-tube is 20-90 weight %.
4. lithium ion secondary battery positive electrode according to claim 2, wherein, the diameter of described carbon nano-tube is that 1-100 nanometer, draw ratio are not less than 100.
5. lithium ion secondary battery positive electrode according to claim 4, wherein, the diameter of described carbon nano-tube is that 5-90 nanometer, draw ratio are 100-10000.
6. lithium ion secondary battery positive electrode according to claim 1, wherein, described positive active material is Li
xNi
1-yCo
yO
2, Li
xMn
2-yB
yO
2, wherein B is a transition metal or nonmetal, 0.9≤x≤1.1,0≤y≤1.
7. lithium rechargeable battery, this battery comprises battery container, pole piece and electrolyte, described pole piece and electrolyte are sealed in the battery container, described pole piece comprises positive pole, negative pole and the barrier film between positive pole and negative pole, wherein, any described lithium ion secondary battery positive electrode among the described just very claim 1-6.
8. lithium rechargeable battery according to claim 7, wherein, described negative pole comprises collector and the negative material that loads on the collector, this negative material contains negative electrode active material, conductive agent and adhesive, the average grain diameter D of described negative electrode active material
50Be the 5-15 micron, and the particle size distribution σ of negative electrode active material satisfies:
9. lithium rechargeable battery according to claim 7, wherein, described conductive agent contains the carbon nano-tube of 20-90 weight %.
10. lithium rechargeable battery according to claim 8, wherein, the diameter of described carbon nano-tube is that 5-90 nanometer, draw ratio are 100-10000.
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