CN101154730A - Lithium ion battery anode material and anode and lithium ion battery containing the said material - Google Patents
Lithium ion battery anode material and anode and lithium ion battery containing the said material Download PDFInfo
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- CN101154730A CN101154730A CNA2006101401175A CN200610140117A CN101154730A CN 101154730 A CN101154730 A CN 101154730A CN A2006101401175 A CNA2006101401175 A CN A2006101401175A CN 200610140117 A CN200610140117 A CN 200610140117A CN 101154730 A CN101154730 A CN 101154730A
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Abstract
The invention discloses a lithium ion battery anode material, which comprises an anode active matte, a conductor and an adhesive, wherein, the conductor contains a carbon nanometer pipe and a conductive graphite. The adhesive contains an alkene alcohol group polymer. In the lithium ion battery anode material of the invention, with the adhesive, the water-base adhesive alkene alcohol group polymer is adopted. The carbon nanometer pipe and the conductive graphite are adopted as the conductor, so that the water can be used as solvent in preparing anode slip by the material, thereby being favorable for environment protection and saving production cost on one hand and greatly reducing the inner resistance of the anode and lithium ion battery by the material on the other hand. Further, the multiplying power discharging performance and circulation performance are greatly improved.
Description
Technical field
The invention relates to a kind of anode material for lithium-ion batteries and the positive pole and the lithium ion battery that contain this material.
Background technology
Lithium ion battery is divided into liquid lithium ion battery (LIB) and polymer Li-ion battery (PLIB).Lithium ion battery mainly comprises pole piece, nonaqueous electrolytic solution and battery container, described pole piece and nonaqueous electrolytic solution are sealed in the battery container, described pole piece comprises anode, negative pole and barrier film, described positive pole comprises collector body and coating and/or is filled in positive electrode on the collector body that described positive electrode comprises positive active material, conductive agent and adhesive.The preparation method of anode comprise will contain the slurry of positive active material, conductive agent and adhesive and solvent apply and/or be filled on the collector body, drying, pressing mold or pressing mold not.Adhesive will be bonded together between active material and the collector body and between the active material.
At present, lithium rechargeable battery adopts polyvinylidene fluoride (PVDF) as adhesive, uses organic compound such as N-methyl pyrrolidone (NMP), N, and dinethylformamide (DMF), dimethyl sulfoxide (DMSO) (DMSO) etc. are as the solvent of PVDF.As US 6426165, US 5246796 employing PVDF is all disclosed as anodal adhesive.On the one hand, polyvinylidene fluoride itself is a kind of fiber, in order to guarantee that positive active material, conductive agent can effectively be bonded on the conducting base, the amount that will guarantee adhesive polyvinylidene fluoride (PVDF) is at the 3-5 of positive active material weight %, but the amount of PVDF too much can cause positive active material to be capped, thereby causes the function of positive active material to be difficult to effective performance, the utilance of positive active material descends, and battery capacity descends; If the amount of PVDF is very few, cause positive electrode material to break away from from collector body easily, cause battery life to descend.On the other hand, the boiling point of above-mentioned organic compound as solvent is higher, when film-making, because the boiling point height of above-mentioned organic solvent, be not easy drying, therefore after being coated on slurry on the collector, need under 120-135 ℃ of temperature, solvent could be dried the baking temperature height, bring inconvenience for the production operation personnel, and described organic solvent is harmful.
Compare with above-mentioned solvent type adhesive, that water-based adhesives has is pollution-free, cost is low, do not fire, characteristics such as safe in utilization.Research about water-based adhesives the earliest is mainly used in negative pole, a kind of water-based adhesives that uses butadiene-styrene rubber (SBR) as bonding agent is disclosed as JP5-74461, but owing to there are two keys on the SBR main chain, and positive pole is in a strong oxidation environment in charge and discharge process, therefore with this kind adhesive application during in positive pole, SBR in charge and discharge process the two keys on the main chain can and electrolyte in organic substance react, cause deterioration of battery, have a strong impact on the serviceability of battery.
Also some patent disclosures have been arranged in addition and used the positive pole of water system binding agent, but make water as solvent during owing to anodal batching, make acetylene black and the carbon black that add cause the particle of slurry bigger because poly-group phenomenon takes place in water as conductive agent, at when coating pole piece rough surface, have a strong impact on the performance of battery.Though use graphite the slurry aggregation phenomenon can not occur, be to stay in the hole of active material and contact the formation conductive network with collision between the particle by particle as the graphite of electric conducting material.Thisly cross some contact and the conductive capability of the electron propagation ducts that forms only depends on the collision probability between the particle by the graininess conductor dbus.And how many this collision probabilities is directly proportional with the quantity of particle.Therefore in the prior art, the conductivity that increase electrode has only the method by using a large amount of conductive agents to realize.But the ratio that increases conductive agent will certainly reduce the amount of positive active material, thereby limit battery capacity and energy density.And the resistance of above-mentioned battery is big, multiplying power discharging property and cycle performance are relatively poor.
Though bibliographical information is arranged, use fibrous electric conducting material such as carbon nano-tube, carbon fiber etc. as conductive agent, can between positive active material, form conductive network preferably, thereby effectively reduce the internal resistance of battery, use more a spot of conductive agent can realize enough conductivity.But when using above-mentioned fibrous electric conducting material as conductive agent, the multiplying power discharging property of battery and cycle performance still are not very good.
Summary of the invention
The objective of the invention is in order to overcome existing lithium ion battery multiplying power discharging property and the relatively poor defective of cycle performance, provide a kind of and can make the battery positive electrode with good lithium ion battery multiplying power discharging property and cycle performance and the positive pole and the lithium ion battery that contain this positive electrode.
Anode material for lithium-ion batteries provided by the invention contains positive active material, conductive agent and adhesive, and wherein, described conductive agent contains carbon nano-tube and electrically conductive graphite, and described adhesive contains the enol based polyalcohol.
Lithium ion cell positive provided by the invention comprises collector body and the positive electrode that loads on the collector body, and wherein, described positive electrode is an anode material for lithium-ion batteries provided by the invention.
Lithium ion battery provided by the invention comprises pole piece, nonaqueous electrolytic solution and battery container, described pole piece and nonaqueous electrolytic solution are sealed in the battery container, described pole piece comprises positive pole, negative pole and barrier film, wherein, and described lithium ion cell positive just very provided by the invention.
In the anode material for lithium-ion batteries provided by the invention, owing to adopt aqueous binder enol based polyalcohol as adhesive, employing contains carbon nano-tube and electrically conductive graphite as conductive agent, make that this material can be with water as solvent when being prepared into anode sizing agent, thereby one side helps environmental protection and saves production cost, can also make on the other hand and adopt the positive pole that this material makes and the internal resistance of lithium ion battery to reduce greatly, multiplying power discharging property and cycle performance also improve greatly.
Embodiment
According to anode material for lithium-ion batteries provided by the invention, although a spot of carbon nano-tube can reduce the internal resistance of the battery that contains this electrode material, and the multiplying power discharging property and the cycle performance of raising battery, but preferable case, total amount with conductive agent is a benchmark, the content of described carbon nano-tube is 10-90 weight %, is preferably 30-80 weight %; The content of described electrically conductive graphite is 10-90 weight %, is preferably 20-70 weight %.
Although the carbon nano-tube of various different-diameters and draw ratio all can realize purpose of the present invention, under the preferable case, the diameter of described carbon nano-tube is the 1-100 nanometer, is preferably the 5-90 nanometer, more preferably the 5-50 nanometer; Draw ratio is not less than 100, for example can be 100-10000.The carbon nano-tube that use has above-mentioned diameter and draw ratio can guarantee to form between the carbon nano-tube better conductive network, thereby further improve the conductivity of positive active material, and, the dispersiveness of carbon nano-tube in water with above-mentioned diameter and draw ratio is better, when the preparation anode sizing agent, be not easy to reunite, and have an imbibition ability preferably, 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.
Because the inhomogeneous and expansion in the repeated charge process of positive active material particle; cause short grained active material to be wrapped up and can't touch the conductive mesh that carbon nano-tube is formed by oarse-grained active material; therefore add the granular pattern electrically conductive graphite and can guarantee to be filled in the hole of granule active material and the formation of bulky grain active material, guarantee all to exist between all active material particles the conductivity of the electrode of electric conducting material assurance preferably than the graphite of granule.Among the present invention, described granular pattern electrically conductive graphite can be conventionally used as the graphite of conductive agent for the lithium ion battery field, and under the preferable case, described electrically conductive graphite is mean particle diameter D
50Flakey electrically conductive graphite for the 1-10 micron.The size of this electrically conductive graphite is suitable with the granular size of positive active material, thereby can enter better between the positive active material particle, further improves the utilance of positive active material.
Except carbon nano-tube and electrically conductive graphite, conductive agent among the present invention can also contain conventional other the various conductive agents that use of anode material for lithium-ion batteries, as in ketjen carbon black, acetylene black, furnace black, carbon fiber VGCF, conductive carbon black and various metallic such as copper particle, the lithium particle one or more.Total amount with conductive agent is a benchmark, and the content of other the various conductive agents except that carbon nano-tube and electrically conductive graphite can be 0-80 weight %, is preferably 5-50 weight %.
Total amount with positive electrode is a benchmark, and the total content of conductive agent can be 0.5-10 weight %, is preferably 1-5 weight %.
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 in conventional adhesive such as the butadiene-styrene rubber class adhesive (SBR), 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 the bad stability in water.The product of alcoholysis degree 80-95% is water-soluble best, can form netted rock-steady 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 utmost point 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.
Can influence the viscosity of positive electrode as the consumption of the cellulose-based polymer of thickener or its slaine,, surpass 5%, the viscosity of anode sizing agent is increased, be not suitable for as coating material if the consumption of cellulose-based polymer is too much.Therefore, under the preferable case, the consumption of described cellulose-based polymer is the 0-5 weight % of positive active material, is preferably 0.1-2 weight %.
In the positive electrode provided by the invention, the content of adhesive can be the binder content of this area routine.Owing to contain the better enol based polyalcohol of caking property as adhesive, therefore the content of adhesive can be lower than the content of conventional adhesive such as PVDF slightly, for example, is benchmark with the total amount of positive electrode, the total content of adhesive can be 0.5-5 weight %, is preferably 1-3 weight %.
According to anode material for lithium-ion batteries provided by the invention, described positive active material can be the positive active material of the embedded removal lithium embedded of this area routine, one or more in the preferred following material: Li
xNi
1-yCoO
2(wherein, 0.9≤x≤1.1,0≤y≤1.0), Li
1+aM
bMn
2-bO
4(wherein ,-0.1≤a≤0.2,0≤b≤1.0, M is a kind of in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur), Li
mMn
2-nB
nO
2(wherein, B is a transition metal, 0.9≤m≤1.1,0≤n≤1.0).The particle diameter of positive active material is generally the 5-15 micron.Total amount with positive electrode is a benchmark, and the content of positive active material can be 85-98.5 weight %.
Because the present invention only relates to the improvement to anode material for lithium-ion batteries, be not particularly limited forming anodal collector body, can be positive electrode collector conventional in the lithium ion battery, in specific embodiments of the present invention, use aluminium foil as positive electrode collector.
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.
The negative pole, barrier film and the nonaqueous electrolytic solution that form lithium ion battery of the present invention 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.
Described negative material can also comprise conductive agent, and described conductive agent is not particularly limited, and 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 and the electrically conductive graphite one or more.Weight with negative electrode active material is benchmark, and the content of described conductive agent is 1-15 weight %, is preferably 2-10 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 polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), the butadiene-styrene rubber (SBR); In general, according to the difference of adhesive therefor kind, be benchmark with the weight of negative electrode active material, the content of adhesive is 0.01-8 weight %, is preferably 0.02-5 weight %.
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.
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 is arranged between positive pole and the negative pole, and it has electrical insulation capability and liquid retainability energy, and described pole piece and nonaqueous electrolytic solution are contained in the battery case together.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 membrane 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 invention will be further described.
Embodiment 1
This embodiment illustrates lithium ion anode material provided by the invention and contains positive pole and the lithium ion battery and their preparation method of this positive electrode.
(1) Zheng Ji preparation
With 100 gram mean particle diameter D
50Be 8 microns LiCoO
2, 2 the gram polyvinyl alcohol (degree of polymerization is 1900, alcoholysis degree is 80%) mix with 40 gram water, and then (diameter is the 10-40 nanometer to restrain carbon nano-tube with 1 gram electrically conductive graphite KS6 (TIMICAL company product), 1, draw ratio is 500, remittance company of heap of stone in Taiwan produces) mix, in de-airing mixer, stir the uniform anode sizing agent of formation afterwards.This anode sizing agent is coated on the aluminium foil equably, 150 ℃ of following oven dry, roll-ins then, cuts and make long 540 millimeters, wide 43.5 millimeters positive plate.Positive electrode content on this positive plate is 6.2 grams.
(2) preparation of negative pole
Mixture, the 4 gram carbon blacks of 100 gram native graphites, 1.0 gram carboxymethyl celluloses and 3 gram butadiene-styrene rubber are joined in the 120 gram water, in de-airing mixer, stir then and form uniform cathode size.This slurry is coated on the Copper Foil equably, then in 90 ℃ of following oven dry, roll-in, cut and make long 500 millimeters, wide 44 millimeters negative plate.The content of the negative material on this negative plate is 2.8 grams.
(3) assembling of battery
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 EC/DMC=1: form nonaqueous electrolytic solution in 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 illustrates lithium ion anode material provided by the invention and contains positive pole and the lithium ion battery and their preparation method of this positive electrode.
(1) Zheng Ji preparation
With 100 gram mean particle diameter D
50Be 12 microns LiCoO
2, 1.05 the gram polyvinyl alcohol (degree of polymerization is 3000, alcoholysis degree is 85%), 1.05 gram thickener CMC and 40 restrain water and mix, and then with 0.5 gram electrically conductive graphite KS6, (diameter is the 20-50 nanometer to 1 gram carbon nano-tube, draw ratio is 150, remittance company of heap of stone in Taiwan produces) mix, in de-airing mixer, stir the uniform anode sizing agent of formation afterwards.This anode sizing agent is coated on the aluminium foil equably, 150 ℃ of following oven dry, roll-ins then, cuts and make long 540 millimeters, wide 43.5 millimeters positive plate.Positive electrode content on this positive plate is 6.2 grams.
(2) preparation of negative pole
According to preparing negative plate with the identical method of the foregoing description 1 step (2).
(3) assembling of battery
Prepare the lithium ion battery A2 of LP043450A type according to the described method of embodiment 1 step (3), different is that positive plate is the positive plate of above-mentioned (1) preparation.
Embodiment 3
This embodiment illustrates lithium ion anode material provided by the invention and contains positive pole and the lithium ion battery and their preparation method of this positive electrode.
(1) Zheng Ji preparation
With 100 gram mean particle diameter D
50Be 15 microns LiCoO
2, 1.6 the gram polyvinyl alcohol (degree of polymerization is 3000, alcoholysis degree is 85%), 1.6 gram thickener CMC and 40 restrain water and mix, and then with 0.2 gram electrically conductive graphite KS6, (diameter is the 10-30 nanometer to 0.8 gram carbon nano-tube, draw ratio is 300, remittance company of heap of stone in Taiwan produces) mix, in de-airing mixer, stir the uniform anode sizing agent of formation afterwards.This anode sizing agent is coated on the aluminium foil equably, 150 ℃ of following oven dry, roll-ins then, cuts and make long 540 millimeters, wide 43.5 millimeters positive plate.Positive electrode content on this positive plate is 6.2 grams.
(2) preparation of negative pole
According to preparing negative plate with the identical method of the foregoing description 1 step (2).
(3) assembling of battery
Prepare the lithium ion battery A3 of LP043450A type according to the described method of embodiment 1 step (3), different is that positive plate is the positive plate of above-mentioned (1) preparation.
Embodiment 4
This embodiment illustrates lithium ion anode material provided by the invention and contains positive pole and the lithium ion battery and their preparation method of this positive electrode.
(1) Zheng Ji preparation
With 100 gram mean particle diameter D
50Be 10 microns LiCoO
2, 2.12 the gram polyvinyl alcohol (degree of polymerization is 3000, alcoholysis degree is 85%), 1.06 gram thickener CMC and 40 restrain water and mix, and then with 2.5 gram electrically conductive graphite KS6, (diameter is the 20-50 micron to 0.5 gram carbon nano-tube, draw ratio is 300, nanometer port, Shenzhen company produces) mix, in de-airing mixer, stir afterwards and form uniform anode sizing agent.This anode sizing agent is coated on the aluminium foil equably, 150 ℃ of following oven dry, roll-ins then, cuts and make long 540 millimeters, wide 43.5 millimeters positive plate.Positive electrode content on this positive plate is 6.2 grams.
(2) preparation of negative pole
According to preparing negative plate with the identical method of the foregoing description 1 step (2).
(3) assembling of battery
Prepare the lithium ion battery A4 of LP043450A type according to the described method of embodiment 1 step (3), different is that positive plate is the positive plate of above-mentioned (1) preparation.
Embodiment 5
This embodiment illustrates lithium ion anode material provided by the invention and contains positive pole and the lithium ion battery and their preparation method of this positive electrode.
Prepare the lithium ion battery A5 of LP043450A type according to the method for embodiment 1, different is, the diameter of carbon nano-tube is the 10-40 micron, and draw ratio is 50.
Embodiment 6
This embodiment illustrates lithium ion anode material provided by the invention and contains positive pole and the lithium ion battery and their preparation method of this positive electrode.
Prepare the lithium ion battery A5 of LP043450A type according to the method for embodiment 1, different is the mean particle diameter D of electrically conductive graphite
50It is 15 microns.
Comparative Examples 1
The lithium ion anode material and the positive pole and lithium ion battery and their preparation method that contain this positive electrode of this Comparative Examples explanation prior art.
Method according to embodiment 1 prepares the reference positive pole and comprises this anodal lithium ion battery, different is, 2 gram polyvinyl alcohol adopt 2 gram PVDF (the luxuriant and rich with fragrance company of atropic commodity, 761#PVDF) replace, 40 gram hydrominings replace with 50 milliliters of N-methyl pyrrolidones (NMP), make the square lithium ion battery AC1 of LP043450A type.
Comparative Examples 2
The lithium ion anode material and the positive pole and lithium ion battery and their preparation method that contain this positive electrode of this Comparative Examples explanation prior art.
Method according to embodiment 1 prepares the reference positive pole and comprises this anodal lithium ion battery, and different is that 1 gram electrically conductive graphite KS6 and 1 gram carbon nano-tube adopt 2 gram carbon nano-tube replacements, make the square lithium ion battery AC2 of LP043450A type.
Comparative Examples 3
The lithium ion anode material and the positive pole and lithium ion battery and their preparation method that contain this positive electrode of this Comparative Examples explanation prior art.
Method according to embodiment 1 prepares the reference positive pole and comprises this anodal lithium ion battery, different is, 1 gram electrically conductive graphite KS6 and 1 gram carbon nano-tube adopt 1 gram acetylene black (super-p, Timical company produces) and 1 gram carbon nano-tube replacement, make the square lithium ion battery AC3 of LP043450A type.
Comparative Examples 4
The lithium ion anode material and the positive pole and lithium ion battery and their preparation method that contain this positive electrode of this Comparative Examples explanation prior art.
Method according to embodiment 1 prepares the reference positive pole and comprises this anodal lithium ion battery, different is, 1 gram electrically conductive graphite KS6 and 1 gram carbon nano-tube adopt 2 gram acetylene blacks (Super-p, Timical company produces) to replace, and make the square lithium ion battery AC4 of LP043450A type.
Comparative Examples 5
The lithium ion anode material and the positive pole and lithium ion battery and their preparation method that contain this positive electrode of this Comparative Examples explanation prior art.
Method according to embodiment 1 prepares the reference positive pole and comprises this anodal lithium ion battery, and different is that 1 gram electrically conductive graphite KS6 and 1 gram carbon nano-tube adopt 2 gram electrically conductive graphite KS6 replacements, make the square lithium ion battery AC5 of LP043450A type.
Embodiment 7-12
The following examples are used to illustrate the positive pole that made by positive electrode provided by the invention and the performance of lithium ion battery.
Lithium ion battery A1, A2, A3, A4, A5 and the A6 that will be made by embodiment 1-6 at room temperature earlier with the current charges of 0.05C 4 hours, seals after 6 hours with the current charges of 0.1C respectively after storing 48 hours under 45 ℃ the environment again.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 with above-mentioned battery in BS-VR internal resistance of cell tester test internal resistance and measure the 3C/0.2C multiplying power discharging property and the cycle performance of each battery respectively according to following method.
3C/0.2C multiplying power discharging property: 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.Shelve after 5 minutes and lie prostrate with 1C current charges to 4.2, rise 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, above-mentioned 3C capacity and 0.2C Capacity Ratio are the 3C/0.2C multiplying power discharging property.
The cycle performance test: 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 1C current discharge to 3.0 volt, shelved 5 minutes then, write down cyclic discharge capacity first.Repeat above step 500 time, obtain the capacity of 500 circulation backs of battery 1C current discharge to 3.0 volt, by capacity sustainment rate before and after the following formula computation cycles:
Capacity sustainment rate=(the 500th cyclic discharge capacity/cyclic discharge capacity) first * 100% capacity sustainment rate is high more, illustrates that the cycle performance of battery is good more, and measurement result is as shown in table 1.
Table 1
| Conductive agent is formed | The internal resistance of cell (milliohm) | 3C/0.2C multiplying power discharging property (%) | Capacity surplus ratio (%) | |||
| Carbon nano-tube | Graphite | Acetylene black | ||||
| Embodiment 1 | 1 | 1 | - | 40 | 96.2 | 85.3 |
| Embodiment 2 | 1 | 0.5 | - | 40 | 95.4 | 83.9 |
| Embodiment 3 | 0.8 | 0.2 | - | 43 | 94.3 | 83.5 |
| Embodiment 4 | 0.5 | 2.5 | - | 42 | 94.5 | 82.9 |
| Embodiment 5 | 1 | 1 | - | 46 | 90.4 | 80.3 |
| Embodiment 6 | 1 | 1 | - | 44 | 90.3 | 77.4 |
| Comparative Examples 1 | 1 | 1 | - | 46 | 85.8 | 72.9 |
| Comparative Examples 2 | 2 | - | - | 47 | 85.6 | 70.1 |
| Comparative Examples 3 | 1 | - | 1 | 48 | 88.3 | 74.9 |
| Comparative Examples 4 | - | - | 2 | 49 | 53.2 | 76.1 |
| Comparative Examples 5 | - | 2 | - | 50 | 49.4 | 72.9 |
From the result shown in the table 1 as can be seen, lithium ion battery provided by the invention is compared with reference cell, have good multiplying power discharging property and cycle performance, and the internal resistance of cell reduces obviously.In addition, compare with embodiment 1, embodiment 5 not in preferable range, causes the internal resistance of cell to rise to some extent because the draw ratio of carbon nano-tube is too little, and multiplying power discharging property and cycle performance descend; 6 of embodiment can not effectively enter between the positive active material particle because the particle of electrically conductive graphite is too big, make that also the internal resistance of cell rises to some extent, and multiplying power discharging property and cycle performance descend.
Claims (10)
1. anode material for lithium-ion batteries, this material contains positive active material, conductive agent and adhesive, it is characterized in that, and described conductive agent contains carbon nano-tube and electrically conductive graphite, and described adhesive contains the enol based polyalcohol.
2. positive electrode according to claim 1 wherein, is a benchmark with the total amount of positive electrode, and the content of positive active material is 85-98.5 weight %, and the content of conductive agent is 0.5-10 weight %, and the content of adhesive is 0.5-5 weight %.
3. positive electrode according to claim 1 and 2 wherein, is a benchmark with the total amount of conductive agent, and the content of described carbon nano-tube is 10-90 weight %, and the content of described electrically conductive graphite is 10-90 weight %.
4. positive electrode according to claim 3, wherein, the diameter of described carbon nano-tube is that 1-100 nanometer, draw ratio are not less than 100.
5. 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. according to claim 1 or 3 described positive electrodes, wherein, described electrically conductive graphite is mean particle diameter D
50Flakey electrically conductive graphite for the 1-10 micron.
7. positive electrode according to claim 1 and 2 wherein, is a benchmark with the total amount of adhesive, and the content of described enol based polyalcohol is 20-80 weight %.
8. positive electrode according to claim 7, wherein, the degree of polymerization of described enol based polyalcohol is 1700-5000, and alcoholysis degree is 70-99%, and described enol based polyalcohol is selected from one or more in polyvinyl alcohol, POLYPROPYLENE GLYCOL, the polyisobutene alcohol.
9. lithium ion cell positive, this positive pole comprise collector body and load on positive electrode on the collector body, it is characterized in that described positive electrode is any described positive electrode among the claim 1-8.
10. lithium ion battery, this battery comprises pole piece, nonaqueous electrolytic solution and battery container, and described pole piece and nonaqueous electrolytic solution are sealed in the battery container, and described pole piece comprises positive pole, negative pole and barrier film, it is characterized in that the described positive pole of described just very claim 9.
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