CN101174682A - Anode and method for producing the same and lithium ion secondary battery - Google Patents
Anode and method for producing the same and lithium ion secondary battery Download PDFInfo
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- CN101174682A CN101174682A CNA2006101379129A CN200610137912A CN101174682A CN 101174682 A CN101174682 A CN 101174682A CN A2006101379129 A CNA2006101379129 A CN A2006101379129A CN 200610137912 A CN200610137912 A CN 200610137912A CN 101174682 A CN101174682 A CN 101174682A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a battery anode, which comprises a collecting body and an anode material that is coated on the collecting body; the anode material comprises an anode active substance and an adhesion agent, wherein, the anode active substance is a mixture of an anode active substance A and an anode active substance B; the particle diameter of the anode active substance A is larger than that of the anode active substance B; the difference between the median size D50 of the anode active substance A and the anode active substance B is 3 to 10 micron; the specific capacity of the anode active substance A is not less than 140 milliampere hour per gram, and the anode active substance B is the anode active substance containing the magnesium. The anode of the present invention has two different anode active substances with different particle diameters; on the premise of not changing the density of the anode material, the mixture of the two anode active substances are realized, so that the capacity of the battery comprising the anode of the present invention is high and the safety is good. The present invention also provides a preparation method of the anode and a lithium-ion secondary battery comprising the anode.
Description
Technical field
The invention relates to a kind of positive pole and preparation method thereof and comprise the battery that this is anodal, specifically, the invention relates to a kind of positive pole and preparation method thereof and comprise the lithium rechargeable battery that this is anodal.
Background technology
Lithium rechargeable battery refers to respectively the ion battery that constitutes as both positive and negative polarity with two compounds that can reversibly embed with the removal lithium embedded ion.Because of its specific energy height, operating voltage height, operating temperature range is wide, self-discharge rate is low, have extended cycle life, pollution-free, in light weight, advantage such as security performance is good, thereby application is extensive.
Lithium rechargeable battery generally includes battery container and is sealed in this battery container interior electrode group and electrolyte; Described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole; Described positive pole comprises positive electrode collector and applies positive electrode on it; Described positive electrode comprises positive active material and adhesive, and selectivity contains conductive agent.Described negative pole comprises negative electrode collector and applies negative material on it; Described negative material comprises negative electrode active material and adhesive.
The positive active material that lithium rechargeable battery is commonly used can be lithium cobalt oxygen, lithium nickel oxygen, lithium manganese oxygen, lithium-nickel-cobalt-oxygen, Li-Ni-Mn-O, lithium manganese cobalt oxygen and Li-Ni-Mn-Co-O, the median particle diameter D of general described positive active material
50Be the 10-15 micron.These positive active materials can be divided into two classes: a class positive active material (as lithium cobalt oxygen, lithium nickel oxygen and lithium-nickel-cobalt-oxygen) specific capacity is not less than 140 MAH/grams, can make the positive electrode of high density, thereby by the battery of such positive active material preparation in the requirement that can satisfy use aspect the battery capacity, but there is potential safety hazard in the poor heat stability by the battery of such positive active material preparation; Another kind of positive active material (as lithium manganese oxygen, lithium manganese cobalt oxygen, Li-Ni-Mn-O and the Li-Ni-Mn-Co-O) Heat stability is good that contains manganese, fail safe is good after making battery, but because the specific capacity of such positive active material is no more than 130 MAH/grams, can't make the positive electrode of high density, thereby make the battery capacity deficiency that makes.
There is the situation for preparing anode with the mixture of the different positive active material of above-mentioned two classes in prior art, but select for use two class positive active material mixtures can make the positive electrode volume density not reach the volume density level that the above-mentioned first kind positive active material of independent use can reach, thereby make battery capacity on the low side.But do not add the second class positive active material, can not play the effect that improves battery security again.
In sum, no matter select single positive active material for use, still select the mixture of different types of positive active material for use, the positive pole of prior art all is difficult to take into account the requirement of battery capacity and fail safe.
Summary of the invention
The objective of the invention is to overcome the shortcoming that existing lithium ion secondary battery positive electrode can not be taken into account battery capacity and battery security, a kind of lithium ion secondary battery capacity height and good positive pole of fail safe of making is provided.
Second purpose of the present invention provides the preparation method of above-mentioned positive pole.
The 3rd purpose of the present invention provides the lithium rechargeable battery that uses above-mentioned positive pole.
The present inventor finds, prior art adopts the prepared positive electrode volume density of the mixture of positive active material of above-mentioned two classes low, is to cause the battery capacity of lithium rechargeable battery and the reason that fail safe can not take into account.The present inventor finds through research, poor by making described two class positive active materials have a particle diameter, this two classes positive active material is arranged on the collector body according to as shown in Figure 1 mode, thereby the positive electrode volume density that comprises two class positive active materials is improved, reach the purpose of improving battery capacity and fail safe simultaneously then.
The invention provides a kind of anode, this positive pole comprises collector and the positive electrode that is coated on this collector; Described positive electrode comprises positive active material and adhesive, and wherein, described positive active material is the mixture of positive active material A and positive active material B; The particle diameter of described positive active material A is greater than the particle diameter of positive active material B; The median particle diameter D of described positive active material A and positive active material B
50Difference is the 3-10 micron; The specific capacity of described positive active material A is not less than 140 MAH/grams, and described positive active material B is the positive active material that contains manganese.
The invention provides the preparation method of above-mentioned anode, this method comprises that the slurry that will contain positive electrode is coated on the collector, dry, calendering, described positive electrode comprises positive active material and adhesive, wherein, described positive active material is the mixture of positive active material A and positive active material B; The particle diameter of described positive active material A is greater than the particle diameter of positive active material B; The median particle diameter D of described positive active material A and positive active material B
50Difference is the 3-10 micron; The specific capacity of described positive active material A is not less than 140 MAH/grams, and described positive active material B is the positive active material that contains manganese.
The present invention also provides a kind of lithium rechargeable battery, and this battery comprises battery container and is sealed in this battery container interior electrode group and electrolyte; Described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, wherein, and described positive pole just very of the present invention.
Because of the present invention just having two kinds of different positive active materials that have the particle diameter difference, do not changing under the anodal volume density prerequisite, can realize the mixing of the positive active material of two class different in kinds, make the battery capacity height and the fail safe that comprise positive pole of the present invention good.The median particle diameter D of lithium cobalt oxygen in the positive active material of the lithium rechargeable battery that is provided as embodiment 1
50Be 15 microns, the median particle diameter D of lithium manganese oxygen
50Be 5 microns, the weight ratio of the two is 7: 3, and the positive active material of Comparative Examples 1 is median particle diameter D
50Be 15 microns lithium cobalt oxygen, the positive active material of Comparative Examples 2 is median particle diameter D
50Be 15 microns lithium cobalt oxygen and lithium manganese oxygen; Under the situation that the positive active material consumption equates, the battery capacity of embodiment 1 reaches 758 milliampere-hours, remain basically stable with 760 milliampere-hours of Comparative Examples 1, and the battery capacity of Comparative Examples 2 only is 679 milliampere-hours; During 200 ℃ of furnace temperature safety tests, the battery of embodiment 1 and Comparative Examples 2 passes through smoothly, and smoldering appears in Comparative Examples 1, the phenomenon of on fire and blast.
Description of drawings
Fig. 1 is the positive active material distribution schematic diagram;
Fig. 2 is that negative pole tow sides electrode material applies the effective area schematic diagram.
Description of reference numerals:
1---positive active material A 2---positive active material B
3---collector body
Embodiment
Anode provided by the invention comprises collector and the positive electrode that is coated on this collector; Described positive electrode comprises positive active material and adhesive, and wherein, described positive active material is the mixture of positive active material A and positive active material B; The particle diameter of described positive active material A is greater than the particle diameter of positive active material B; The median particle diameter D of described positive active material A and positive active material B
50Difference is the 3-10 micron; The specific capacity of described positive active material A is not less than 140 MAH/grams, and described positive active material B is the positive active material that contains manganese.
Described positive active material A specific capacity is not less than 140 MAH/grams, can make the positive electrode of high density, thereby by the battery of such positive active material preparation in the requirement that can satisfy use aspect the battery capacity, but poor heat stability by the battery of such positive active material preparation, the battery of making very fast (20 minutes) leakage in 150 ℃ of furnace temperature tests is smoldered on fire, has potential safety hazard.Described positive active material B is the positive active material that contains manganese, Heat stability is good, make battery after fail safe good, can stand the test of 300 ℃ of furnace temperature, but, can not satisfy the requirement of battery capacity because the specific capacity of such positive active material is no more than 130 MAH/grams.
Described median particle diameter D
50, be the value of expression sample average granule size, promptly there is 50% particle diameter to be worth in institute's test sample product greater than this, 50% particle diameter is worth less than this.The median particle diameter D of prior art positive active material
50Be generally the 10-15 micron, the positive active material particle is general spherical in shape or subsphaeroidal, when being prepared into positive pole, has the space between the particle of positive active material.The particle diameter of positive active material A is greater than the particle diameter of positive active material B, i.e. the median particle diameter D of positive active material A
50Greater than positive active material B median particle diameter D
50As shown in Figure 1, as the median particle diameter D of described positive active material A and positive active material B
50When difference reaches the 3-10 micron, median particle diameter D
50Little positive active material B may reside in the space that forms between the positive active material A particle.Thereby the particle of the particle of positive active material A and positive active material B can not reduce the volume density of positive electrode when being mixed with positive pole.The present invention only defines the median particle diameter difference of two kinds of positive active materials, and the median particle diameter of positive active material be there is no special requirement, the median particle diameter D of preferred described positive active material A
50Be the 10-15 micron, more preferably the 11-14 micron; The median particle diameter D of described positive active material B
50Be the 5-9 micron, more preferably the 6-8 micron.
The ratio of described arbitrarily positive active material A and positive active material B can both reach goal of the invention of the present invention, promptly can take into account the capacity and the fail safe of battery simultaneously.Because the ratio of positive active material A is high more, the battery capacity of making battery is big more, the weight content of therefore preferred positive active material A is greater than the weight content of positive active material B, and more preferably under the situation, positive active material A and positive active material B weight ratio are 9: 1 to 3: 2.
The volume density of described positive electrode is the compacted density of calendering back positive electrode.The volume density ρ of positive electrode
Press=m/ (s * d
Press), wherein m is for rolling the anodal total weight that goes up positive electrode in back, and s is for rolling the effective area that the back positive electrode covers positive electrode collector, d
PressThickness for positive pole calendering back positive electrode material layer.The effective area (S) that described positive electrode covers positive electrode collector is as shown in Figure 2: blank parts does not cover the positive electrode collector surface of positive electrode after for calendering, dash area is for still covering the positive electrode collector surface of positive electrode after rolling, anodal width is W, total length is L, the length of blank parts is respectively L1 and L2, the length of dash area is respectively (L-L1) and (L-L2), then effective area S=[(L-L1)+(L-L2)]/2 * W.
Described positive active material A can be preferably the positive active material that specific capacity is not less than 140 MAH/grams for the high positive active material of existing specific capacity, for example, can be selected from lithium cobalt oxygen, lithium nickel oxygen and the lithium-nickel-cobalt-oxygen one or more.Described positive active material B is the existing positive active material that contains manganese, for example is Li
mMn
2-nB
nO
2And/or Li
1+aM
bMn
2-bO
4Wherein, 0.9≤m≤1.1,0≤n≤1.5,-0.1≤a≤0.2,0≤b≤1.5, B is one or more in the transition metal, M is one or more in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur, more preferably is selected from lithium manganese oxygen, Li
mMn
2-nB
nO
2(wherein, 0.9≤m≤1.1,0＜n≤1.0, B is one or more in lithium, aluminium, iron, cobalt, the nickel element) and Li
1+aM
bMn
2-bO
4In (wherein ,-0.1≤a≤0.2,0＜b≤1.0, M is one or more in lithium, aluminium, iron, cobalt, the nickel element) one or more.
Positive pole of the present invention has no particular limits adhesive, can adopt known in the art all can be used for the adhesive of lithium rechargeable battery.Preferred described adhesive is the mixture of hydrophobicity adhesive and hydrophilic adhesive.The ratio of described hydrophobicity adhesive and hydrophilic adhesive has no particular limits, and can determine according to actual needs, and for example, the part by weight of hydrophilic adhesive and hydrophobicity adhesive can be 0.3: 1-1: 1.Described adhesive can use with the aqueous solution or emulsion form, also can use with solid form, preferably use with the aqueous solution or emulsion form, have no particular limits the concentration of described hydrophilic adhesive solution and the concentration of described hydrophobicity adhesive agent emulsion this moment, the viscosity that can be coated with according to the slurry of positive pole that will prepare and cathode size and the requirement of operability are adjusted flexibly to this concentration, the concentration of for example described hydrophilic adhesive solution can be 0.5-4 weight %, and the concentration of described hydrophobicity adhesive agent emulsion can be 10-80 weight %.Described hydrophobicity adhesive can be polytetrafluoroethylene, butadiene-styrene rubber or their mixture.Described hydrophilic adhesive can be hydroxypropyl methylcellulose, sodium carboxymethylcellulose, hydroxyethylcellulose, polyvinyl alcohol or their mixture.In described adhesive preferably polyethylene alcohol, polytetrafluoroethylene, CMC and the butadiene-styrene rubber one or more.The content of described adhesive is the 0.01-8 weight % of positive active material, is preferably 1-5 weight %.
Described collector can be a various collector known in those skilled in the art, and as aluminium foil, Copper Foil, nickel plated steel strip etc., the present invention selects for use aluminium foil to make collector.
Positive pole provided by the invention can also optionally contain the common conductive agent that contains in the prior art positive electrode.Because conductive agent is used to increase the conductivity of electrode, reduce the internal resistance of battery, so the present invention preferably contains conductive agent.Described conductive agent can be selected from one or more in conductive carbon black, acetylene black, nickel powder, copper powder and the electrically conductive graphite.The content of described conductive agent and kind are conventionally known to one of skill in the art, for example, are benchmark with the positive electrode, and the content of conductive agent is generally 0.5-15 weight %, is preferably 1-6 weight %.
The preparation method of anode provided by the invention comprises that the slurry that will contain positive electrode is coated on the collector, drying, calendering, described positive electrode comprises positive active material and adhesive, wherein, described positive active material is the mixture of positive active material A and positive active material B; The particle diameter of described positive active material A is greater than the particle diameter of positive active material B; The median particle diameter D of described positive active material A and positive active material B
50Difference is the 3-10 micron; The specific capacity of described positive active material A is not less than 140 MAH/grams, and described positive active material B is the positive active material that contains manganese.
Prepare positive pole of the present invention, the median particle diameter D of preferred described positive active material A
50Be the 10-15 micron, more preferably the 11-14 micron; The median particle diameter D of described positive active material B
50Be the 5-9 micron, more preferably the 6-8 micron; The weight ratio of described positive active material A and positive active material B is 9: 1 to 3: 2; Described positive active material A can be preferably the positive active material that is not less than 140 MAH/grams for the high positive active material of existing specific capacity, for example, can be selected from lithium cobalt oxygen, lithium nickel oxygen and the lithium-nickel-cobalt-oxygen one or more.Described positive active material B is the existing positive active material that contains manganese, for example is Li
mMn
2-nB
nO
2And/or Li
1+aM
bMn
2-bO
4Wherein, 0.9≤m≤1.1,0≤n≤1.5,-0.1≤a≤0.2,0≤b≤1.5, B is one or more in the transition metal, M is one or more in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur, more preferably is selected from lithium manganese oxygen, Li
mMn
2-nB
nO
2(wherein, 0.9≤m≤1.1,0＜n≤1.0, B is one or more in lithium, aluminium, iron, cobalt, the nickel element) and Li
1+aM
bMn
2-bO
4In (wherein ,-0.1≤a≤0.2,0＜b≤1.0, M is one or more in lithium, aluminium, iron, cobalt, the nickel element) one or more; With described positive active material is benchmark, and the content of described adhesive is 0.01-8 weight %; Can also contain with the positive electrode is benchmark, and content is the conductive agent of 0.5-15 weight %; Described conductive agent can be selected from one or more in conductive carbon black, acetylene black, nickel powder, copper powder and the electrically conductive graphite.
The described slurry that contains positive electrode can blended anode material and solvent preparation, the solvent that is used to prepare the slurry that contains positive electrode can be selected from conventional solvent, as being selected from N-methyl pyrrolidone (NMP), N, dinethylformamide (DMF), N, one or more in N-diethylformamide (DEF), methyl-sulfoxide (DMSO), oxolane (THF) and water and the alcohols.The consumption of solvent can be coated on the described collector described slurry and gets final product.In general, the consumption of solvent is that to make the concentration of positive active material in the slurry be 40-90 weight %, is preferably 50-85 weight.The known coated weight that can control described slurry by the thickness of control coating slurry of those skilled in the art; Solvent in the slurry can be removed in follow-up battery step (as drying etc.).
The same with prior art, the preparation method of described positive pole is included on the positive electrode collector and applies the slurry that contains the conductive agent that positive active material, adhesive and selectivity contain, drying, and calendering promptly gets anodal after the cut-parts.Described drying usually under vacuum condition at 50-160 ℃, carry out under preferred 80-150 ℃.Described calendering can be adopted this area rolling condition commonly used, such as the 0.5-3.0 MPa.Described cut-parts are as well known to those skilled in the art, after calendering is finished, cut according to the anodal size of prepared battery request, obtain positive pole.
Lithium rechargeable battery provided by the invention comprises battery container and is sealed in this battery container interior electrode group and electrolyte; Described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, wherein, and described positive pole just very of the present invention.Because the present invention only relates to the improvement to the prior art lithium ion secondary battery positive electrode, therefore other The Nomenclature Composition and Structure of Complexes to lithium rechargeable battery has no particular limits.
For example, consisting of of negative pole is conventionally known to one of skill in the art, and in general, negative pole comprises conducting base and coating and/or is filled in negative material on the conducting base.Described conducting base is conventionally known to one of skill in the art, for example can be selected from aluminium foil, Copper Foil, nickel plated steel strip, the Punching steel strip one or more.Described negative active core-shell material is conventionally known to one of skill in the art, it comprises negative electrode active material and adhesive, described negative electrode active material can be selected from the negative electrode active material of lithium rechargeable battery routine, as in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal, the silicon alloy one or more.Described adhesive can be selected from the adhesive of lithium rechargeable battery routine, as in polyvinyl alcohol, polytetrafluoroethylene, CMC (CMC), the butadiene-styrene rubber (SBR) one or more.In general, the content of described adhesive is the 0.5-8 weight % of negative electrode active material, is preferably 2-5 weight %.
The solvent that is used to prepare cathode size of the present invention can be selected from conventional solvent, as being selected from N-methyl pyrrolidone (NMP), N, dinethylformamide (DMF), N, one or more in N-diethylformamide (DEF), methyl-sulfoxide (DMSO), oxolane (THF) and water and the alcohols.The consumption of solvent can be coated on the described collector described slurry and gets final product.In general, the consumption of solvent is that to make the concentration of electrode active material in the slurry be 40-90 weight %, is preferably 50-85 weight %.
Described barrier film has electrical insulation capability and liquid retainability energy, is arranged between positive pole and the negative pole, and is sealed in the battery case with positive pole, negative pole and electrolyte.Described barrier film can be the general various barrier films in this area, such as by those skilled in the art in the modified poly ethylene felt of respectively producing the trade mark, modified polypropene felt, ultra-fine fibre glass felt, vinylon felt or the nylon felt of known each manufacturer production and wettability microporous polyolefin film through welding or the bonding composite membrane that forms.
Described electrolyte is this area electrolyte commonly used, as the mixed solution of electrolyte lithium salt and nonaqueous solvents.Electrolyte lithium salt is selected from lithium hexafluoro phosphate (LiPF
6), in lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and the fluorocarbon based sulfonic acid lithium one or more.Organic solvent can be selected from chain acid esters and ring-type acid esters mixed solution, wherein the chain acid esters can be fluorine-containing for dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other, sulfur-bearing or contain at least a in the chain organosilane ester of unsaturated bond.The ring-type acid esters can (γ-BL), sultone and other be fluorine-containing, sulfur-bearing or contain at least a in the ring-type organosilane ester of unsaturated bond for ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton.In the described electrolyte, the concentration of electrolyte lithium salt is generally the 0.1-2 mol, is preferably the 0.8-1.2 mol.
Unless stated otherwise, all kinds of solvents of the present invention and reagent are commercially available analytical reagent.
The present invention is described further below in conjunction with embodiment.
Embodiment 1
Present embodiment illustrates positive pole provided by the invention and preparation method thereof and comprises the lithium rechargeable battery that this is anodal.
(1) Zheng Ji preparation
30 gram polyvinylidene fluoride (PVDF) are dissolved in about 500 gram N-methyl pyrrolidone (NMP) solvents make binder solution, the median particle diameter D that will mix in advance then
50Be 658 gram lithium cobalt oxygen (Japanese three morals), the median particle diameter D of 15 microns (positive active material A detects through laser particle analyzer)
50The 282 gram lithium manganese oxygen (Yuxi, Yunnan) that are 5 microns (positive active material B detects through laser particle analyzer) join in the above-mentioned solution with the acetylene black powder that 30 grams serve as conductive agent, fully mix and make anode sizing agent; With tensile pulp machine this anode sizing agent is coated to thick 18 microns aluminium foil two sides equably.Through 125 ℃ of vacuum and heating dryings 1 hour, calendaring molding under 2.0 MPa pressure, cut-parts make the positive pole of millimeter (wide) * 130,360 millimeters (length) * 43.5 micron (thick), the volume density of the positive electrode that this is anodal is 3.6 gram/cubic centimetres, contains 5.42 positive active materials that restrain on the every positive pole.
(2) preparation of negative pole
(Kynoar (PVDF) that serves as adhesive with 40 grams fully mixes native graphite for soddif commodity, DAG22) powder 960 grams, is dissolved into about 500 grams and serves as in the N-methyl pyrrolidone of solvent, fully mixes and makes cathode size.With tensile pulp machine this cathode size is coated to the two sides that thickness is 10 microns the Copper Foil that serves as collector body equably.Through 125 ℃ of vacuum and heating dryings 1 hour, two rod milling train rolling formations.Cut-parts make the negative pole of millimeter (wide) * 130,330 millimeters (length) * 44.5 micron (thick), contain 2.25 graphite that restrain on the every negative pole.
(3) assembling of battery
To include in after positive pole, barrier film, negative pole lamination successively and the winding in 4.2 millimeters * 30 millimeters * 48 millimeters the square aluminum hull.
To contain 1 mole lithium hexafluoro phosphate (LiPF
6) ethylene carbonate: the Methylethyl carbonic ester: diethyl carbonate (EC/EMC/DEC) volume ratio be 1: 1: 1 electrolyte about 2.4 the gram, inject above-mentioned battery.The sealed cell aluminum hull can obtain lithium rechargeable battery of the present invention.
Comparative Examples 1
This Comparative Examples illustrates positive pole of prior art and preparation method thereof and comprises the lithium rechargeable battery that this is anodal.
Method according to embodiment 1 prepares positive pole and comprises the battery that this is anodal, and different is that the positive active material of selecting for use is 940 gram median particle diameter D
50Be 15 microns lithium cobalt oxygen, the volume density of the positive electrode of gained positive pole is 3.6 gram/cubic centimetres, contains the 5.47 lithium cobalt oxygen that restrain on the every positive pole.
Comparative Examples 2
This Comparative Examples illustrates positive pole of prior art and preparation method thereof and comprises the lithium rechargeable battery that this is anodal.
Method according to embodiment 1 prepares positive pole and comprises the battery that this is anodal, and different is that the positive active material of selecting for use is 658 gram lithium cobalt oxygen and 282 gram lithium manganese oxygen, the median particle diameter D of the two
50Be 15 microns, the volume density of the positive electrode of gained positive pole is 3.2 gram/cubic centimetres, contains 5.07 positive active materials that restrain on the every positive pole.
Embodiment 2-6
Embodiment illustrates positive pole provided by the invention and preparation method thereof and comprises the lithium rechargeable battery that this is anodal.
Method according to embodiment 1 prepares positive pole and comprises the battery that this is anodal, and different is the proportioning of positive active material and median particle diameter D
50, as shown in table 1 below.
Table 1
Battery performance test:
(1) furnace temperature security test
The battery that makes with embodiment 1-6 and Comparative Examples 1-2, use BS-9300 (R) secondary cell device for detecting performance, electric current with 200 milliamperes (0.2C) charges to 3.8 volts to mesuring battary, shelved 5 minutes, be discharged to 3.0V in order to 1000 milliamperes (1C) then, shelved again 5 minutes, with 200 milliamperes of (0.2C) constant current charge to 4.2 volts.Then the positive pole of battery and negative pole each point are burn-on one 0.15 * 4 * 60 millimeters nickel strap; With the high temperature adhesive plaster thermocouple probe of digital display thermometer is fixed in the middle of the battery surface, then battery is put into the approaching baking oven of initial temperature and room temperature, make high temperature wire one end and battery just/the negative pole end nickel strap links to each other, the other end is drawn baking oven, with universal instrument just/negative test pencil links to each other.Open convection oven and picking up counting simultaneously, make baking oven be warming up to 150 ℃ (or 170 ℃ or 200 ℃), and after 150 ± 2 ℃ (or 170 ± 2 ℃ or 200 ± 2 ℃) keep 10 minutes down, stop test with 5 ± 2 ℃/minute speed.When opening the baking oven power supply, write down the situation of change of temperature, cell voltage and the furnace temperature of battery surface every one minute, observe simultaneously whether battery leakage, breach take place, is smoldered, blast, phenomenon on fire, the time that emphasis recording exceptional phenomenon takes place and the maximum temperature of battery surface at that time.Battery does not take place during to the EOT end of test unusual, is considered as by the furnace temperature security test.
Measurement result is as shown in table 2.
Table 2
From the result shown in the table 2 as can be seen, the furnace temperature fail safe of lithium rechargeable battery provided by the invention is better than the Comparative Examples 1 that only contains lithium cobalt oxygen greatly, and contains median particle diameter D
50The Comparative Examples 2 that is 15 microns lithium cobalt oxygen and lithium manganese oxygen is suitable.
(2) battery capacity test
To the battery that the foregoing description 1-6 and Comparative Examples 1-2 make, carry out the battery capacity test respectively.Test environment is normal temperature, relative humidity 25-85%, and every kind of embodiment or Comparative Examples are measured 15 batteries respectively.Assay method is as follows:
Use BS-9300 (R) secondary cell device for detecting performance, electric current with 200 milliamperes (0.2C) charges to 3.8 volts to mesuring battary, shelved 5 minutes, be discharged to 3.0V in order to 1000 milliamperes (1C) then, shelved again 5 minutes, with 200 milliamperes of (0.2C) constant current charge to 4.2 volts, then with 4.2 volts of constant voltage charges, charging 20 milliamperes of cut-off currents (0.02C).The battery of substituting the bad for the good is lied prostrate with 200 milliamperes of (0.2C) constant-current discharges to 3.0, and the discharge capacity that records thus is the 0.2C discharge capacity.
Measurement result is as shown in table 3.
Table 3
| Embodiment or Comparative Examples | Battery average size (milliampere-hour) |
| Embodiment 1 | 758 |
| Comparative Examples 1 | 760 |
| Comparative Examples 2 | 679 |
| Embodiment 2 | 751 |
| Embodiment 3 | 754 |
| Embodiment 4 | 752 |
| Embodiment 5 | 756 |
| Embodiment 6 | 761 |
From the result shown in the table 3 as can be seen, the lithium rechargeable battery of use mixed cathode active material provided by the invention, its battery capacity is suitable with the simple Comparative Examples 1 of lithium cobalt oxygen of using, significantly better than containing median particle diameter D
50Be the Comparative Examples 2 of 15 microns lithium cobalt oxygen and lithium manganese oxygen.
Claims (17)
1. anode, this positive pole comprise collector and are coated in positive electrode on this collector; Described positive electrode comprises positive active material and adhesive, it is characterized in that, described positive active material is the mixture of positive active material A and positive active material B; The particle diameter of described positive active material A is greater than the particle diameter of positive active material B; The median particle diameter D of described positive active material A and positive active material B
50Difference is the 3-10 micron; The specific capacity of described positive active material A is not less than 140 MAH/grams, and described positive active material B is the positive active material that contains manganese.
2. anode according to claim 1, wherein, the median particle diameter D of described positive active material A
50Be the 10-15 micron; The median particle diameter D of described positive active material B
50Be the 5-9 micron.
3. anode according to claim 1, wherein, the weight ratio of described positive active material A and positive active material B is 9: 1 to 3: 2.
4. according to any described anode among the claim 1-3, wherein, described positive active material A is selected from one or more in lithium cobalt oxygen, lithium nickel oxygen and the lithium-nickel-cobalt-oxygen; Described positive active material B is Li
mMn
2-nB
nO
2And/or Li
1+aM
bMn
2-bO
4, wherein, 0.9≤m≤1.1,0≤n≤1.5 ,-0.1≤a≤0.2,0≤b≤1.5, B is one or more in the transition metal, and M is one or more in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur.
5. anode according to claim 1 wherein, is a benchmark with the positive active material, and the content of described adhesive is 0.01-8 weight %.
6. anode according to claim 1 or 5, wherein, described adhesive is selected from one or more in polyvinyl alcohol, polytetrafluoroethylene, CMC and the butadiene-styrene rubber.
7. anode according to claim 1, wherein, described collector is selected from aluminium foil, Copper Foil or nickel plated steel strip.
8. anode according to claim 1, wherein, it is benchmark that described positive electrode also contains with the positive electrode, content is the conductive agent of 0.5-15 weight %.
9. anode according to claim 8, wherein, described conductive agent is selected from one or more in conductive carbon black, acetylene black, nickel powder, copper powder and the electrically conductive graphite.
10. the preparation method of the described anode of claim 1, this method comprises that the slurry that will contain positive electrode is coated on the collector, dry, calendering, described positive electrode comprises positive active material and adhesive, it is characterized in that described positive active material is the mixture of positive active material A and positive active material B; The particle diameter of described positive active material A is greater than the particle diameter of positive active material B; The median particle diameter D of described positive active material A and positive active material B
50Difference is the 3-10 micron; The specific capacity of described positive active material A is not less than 140 MAH/grams, and described positive active material B is the positive active material that contains manganese.
11. method according to claim 10, wherein, the median particle diameter D of described positive active material A
50Be the 10-15 micron; The median particle diameter D of described positive active material B
50Be the 5-9 micron.
12. method according to claim 10, wherein, the weight ratio of described positive active material A and positive active material B is 9: 1 to 3: 2.
13. according to any described method among the claim 10-12, wherein, described positive active material A is selected from one or more in lithium cobalt oxygen, lithium nickel oxygen and the lithium-nickel-cobalt-oxygen; Described positive active material B is Li
mMn
2-nB
nO
2And/or Li
1+aM
bMn
2-bO
4, wherein, 0.9≤m≤1.1,0≤n≤1.5 ,-0.1≤a≤0.2,0≤b≤1.5, B is one or more in the transition metal, and M is one or more in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur.
14. method according to claim 10, wherein, the slurry that contains positive electrode is the slurry that contains positive electrode and solvent, described solvent is selected from N-methyl pyrrolidone, N, dinethylformamide, N, in N-diethylformamide, methyl-sulfoxide, oxolane and water and the alcohols one or more, this solvent make in the slurry that contains positive electrode, and the content of positive active material is 40-90 weight %; With described positive active material is benchmark, and the content of described adhesive is 0.01-8 weight %.
15. according to claim 10 or 14 described methods, wherein, also containing in the described slurry with the positive electrode is benchmark, content is the conductive agent of 0.5-15 weight %.
16. method according to claim 15, wherein, described conductive agent is selected from one or more in conductive carbon black, acetylene black, nickel powder, copper powder and the electrically conductive graphite.
17. a lithium rechargeable battery, this battery comprise battery container and are sealed in this battery container interior electrode group and electrolyte; Described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, it is characterized in that, any described positive pole among the described just very claim 1-3.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101379129A CN101174682A (en) | 2006-10-30 | 2006-10-30 | Anode and method for producing the same and lithium ion secondary battery |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101379129A CN101174682A (en) | 2006-10-30 | 2006-10-30 | Anode and method for producing the same and lithium ion secondary battery |
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| Publication Number | Publication Date |
|---|---|
| CN101174682A true CN101174682A (en) | 2008-05-07 |
Family
ID=39423027
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|---|---|---|---|
| CNA2006101379129A Pending CN101174682A (en) | 2006-10-30 | 2006-10-30 | Anode and method for producing the same and lithium ion secondary battery |
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| CN (1) | CN101174682A (en) |
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