CN101212070A - Laminated Li-ion secondary battery and method for producing the battery - Google Patents
Laminated Li-ion secondary battery and method for producing the battery Download PDFInfo
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- CN101212070A CN101212070A CNA2006101726181A CN200610172618A CN101212070A CN 101212070 A CN101212070 A CN 101212070A CN A2006101726181 A CNA2006101726181 A CN A2006101726181A CN 200610172618 A CN200610172618 A CN 200610172618A CN 101212070 A CN101212070 A CN 101212070A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a lamination core lithium iron secondary battery. The battery comprises a battery shell and an electrode group and electrolyte which are sealed in the battery shell. The electrode group comprises an anode, a cathode and a diaphragm arranged between the anode and the cathode. The anode comprises an anode current collector and anode material carried on the current collector and the cathode comprises a cathode current collector and cathode material carried on the current collector; the anode current collector and/or the cathode current collector are/is foam metal and the thickness of the foam metal is 0.5-3 millimeter, the tensile strength is not less than 120n/square meter and the porosity is not less than 80 per cent. The lamination core lithium iron secondary battery of the invention, by adopting the foam metal instead of the metal foil as the electrode current collector, increases the strength of the battery electrode and thereby reducing the short circuit rate of the battery as well as increases the specific capacity of the electrode quantity, thus increasing the battery capacity. Furthermore, the electrode material is easier to be drenched by the electrolyte, thus improving the circulation performance of the battery.
Description
Technical field
The invention relates to a kind of battery and preparation method thereof, specifically, the invention relates to a kind of Laminated Type Lithium Ion Secondary Battery and preparation method thereof.
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, and described positive pole comprises plus plate current-collecting body and the positive electrode that loads on this collector, and described negative pole comprises negative current collector and the negative material that loads on this collector.Different according to the fit of battery and anode and negative pole length-width ratio, lithium rechargeable battery can be divided into Laminated Type Lithium Ion Secondary Battery and coiled lithium-ion secondary battery, and wherein the Laminated Type Lithium Ion Secondary Battery heavy-current discharge performance is better.
Laminated Type Lithium Ion Secondary Battery generally adopts the collector of metal forming as electrode, such as using aluminium foil as plus plate current-collecting body, uses Copper Foil as negative current collector.But metal forming quality softness is slided easily between positive pole and the negative pole when assembled battery and is produced short circuit, and in addition, the amount that metal forming can the load electrode material is not high, has the low problem of weight ratio capacity; And electrolyte just is being difficult to soak into/part that negative material and collector body are fitted, and the cycle performance of battery is affected.
In sum, the Laminated Type Lithium Ion Secondary Battery of prior art as collector, exists that short circuit ratio height, weight ratio capacity are low, the defective of cycle performance difference with metal forming.
Summary of the invention
The objective of the invention is to overcome that Laminated Type Lithium Ion Secondary Battery short circuit ratio height, weight ratio capacity are low, the cycle performance difference shortcoming, provide that a kind of Laminated Type Lithium Ion Secondary Battery short circuit ratio is low, weight ratio capacity is high and good cycle.
Second purpose of the present invention provides the preparation method who uses above-mentioned Laminated Type Lithium Ion Secondary Battery.
Prior art generally adopts the collector of metal forming (aluminium foil or Copper Foil) as Laminated Type Lithium Ion Secondary Battery, metal forming quality softness, when assembled battery, slide easily between positive pole and the negative pole and the generation short circuit, the present inventor is surprised to find that, replace the collector of metal forming with foam metal as stacked electrode, produce the percentage of short circuit in the time of not only assembled battery can being significantly reduced, and also can fill electrode material in the hole of foam metal, thereby the foam metal of equivalent can be than the more electrode material of metal forming load, improve the weight ratio capacity of electrode, battery electrolyte can fully soak into the electrode material of foam-metal current collector body in addition, has improved the cycle performance of battery greatly.
The invention provides a kind of Laminated Type Lithium Ion Secondary Battery, 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, described positive pole comprises plus plate current-collecting body and the positive electrode that loads on this collector, described negative pole comprises negative current collector and the negative material that loads on this collector, wherein, described plus plate current-collecting body and/or negative current collector are foam metal, the thickness of described foam metal is the 0.5-3 millimeter, and tensile strength is not less than 120 newton/square centimeters, and porosity is not less than 80%.
The invention provides the preparation method of above-mentioned battery electrode, this method comprises makes plus plate current-collecting body load positive electrode obtain positive pole, make negative current collector load negative material obtain negative pole, to between positive pole and the negative pole barrier film be set, constitute the electrode group, this electrode group is contained in the battery container, inject electrolyte, then that battery container is airtight, wherein, described plus plate current-collecting body and/or negative current collector are foam metal, and the thickness of described foam metal is the 0.5-3 millimeter, tensile strength is not less than 120 newton/square centimeters, and porosity is not less than 80%.
Because Laminated Type Lithium Ion Secondary Battery of the present invention, adopt foam metal to replace metal forming as electrode current collecting body, improve the intensity of battery electrode thereby reduced the battery short circuit rate, increased the electrode weight ratio capacity, thereby improved battery capacity, make the easier infiltration electrode material of electrolyte, thereby improved the cycle performance of battery.Adopt the collector of 6 foamed aluminiums as embodiment 1 battery as anode, the thickness of described foamed aluminium is 1.5 millimeters, tensile strength is 125 newton/square centimeters, porosity is 92%, 29 aluminium foils of the employing of Comparative Examples 1 are as the collector of anode, the battery capacity of embodiment 1 reaches 1380 milliampere-hours, weight ratio capacity reaches 136 milliampere-hour/grams, battery short circuit rate only 1%, circulating, the battery capacity surplus ratio reaches 91% after 400 times, and the battery capacity of Comparative Examples 1 only is 1330 milliampere-hours, and weight ratio capacity only is 129 milliampere-hour/grams, and the battery short circuit rate reaches 10%, and circulating, the battery capacity surplus ratio only is 80% after 400 times.
Embodiment
Laminated Type Lithium Ion Secondary 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, described positive pole comprises plus plate current-collecting body and the positive electrode that loads on this collector, described negative pole comprises negative current collector and the negative material that loads on this collector, wherein, described plus plate current-collecting body and/or negative current collector are foam metal, the thickness of described foam metal is the 0.5-3 millimeter, and tensile strength is not less than 120 newton/square centimeters, and porosity is not less than 80%.
Under the preferable case, the thickness of described foam metal is the 1-2.5 millimeter, and tensile strength is 120-200 newton/square centimeter, and porosity is 90-95%.Described foam metal can be for being preferably foamed aluminium or foam copper as any foam metal of battery afflux liquid, and more preferably plus plate current-collecting body is a foamed aluminium, and negative current collector is a foam copper.The weight ratio of the weight ratio of described positive electrode and plus plate current-collecting body and negative material and negative current collector has shown the amount of the negative material that the amount of the positive electrode that plus plate current-collecting body can load and negative current collector can loads respectively, because the load capacity of metal forming is not high, the weight ratio maximum of the described positive electrode of metal forming and the weight ratio of plus plate current-collecting body and negative material and negative current collector can only reach 7: 1, and the weight ratio of the weight ratio of positive electrode of the present invention and plus plate current-collecting body and/or negative material and negative current collector can be preferably 8: 1 to 10: 1 for greater than 7: 1 to 15: 1.
The preparation method of battery provided by the invention comprises makes plus plate current-collecting body load positive electrode obtain positive pole, make negative current collector load negative material obtain negative pole, just between positive pole and the negative pole barrier film is set, constitute the electrode group, this electrode group is contained in the battery container, inject electrolyte, then that battery container is airtight, wherein, described plus plate current-collecting body and/or negative current collector are foam metal, the thickness of described foam metal is the 0.5-3 millimeter, and tensile strength is not less than 120 newton/square centimeters, and porosity is not less than 80%.The thickness of preferred described foam metal is the 1-2.5 millimeter, and tensile strength is 120-200 newton/square centimeter, and porosity is 90-95%.
The described mode of plus plate current-collecting body load positive electrode that makes is filled or is coated on the plus plate current-collecting body for the slurry that will contain positive electrode, drying, calendering; The described mode of negative current collector load negative material that makes is filled or is coated on the negative current collector for the slurry that will contain negative material, drying, calendering.The preferred described mode of plus plate current-collecting body load positive electrode that makes is coated on the plus plate current-collecting body drying, calendering for the slurry that will contain positive electrode; The described mode of negative current collector load negative material that makes is coated on the negative current collector drying, calendering for the slurry that will contain negative material.The weight ratio that the described slurry that contains positive electrode makes the weight ratio of described positive electrode and plus plate current-collecting body and/or negative material and negative current collector at the coated weight on the plus plate current-collecting body and the described coated weight of slurry on negative current collector that contains negative material is preferably 8: 1 to 10: 1 for greater than 7: 1 to 15: 1.
The described slurry that contains positive electrode comprises positive electrode and dispersant, the described slurry that contains negative material comprises negative material and dispersant, in the mixture of described in theory positive electrode and dispersant and the mixture of described negative material and dispersant, the amount of described dispersant can be infinitely great, consider energy consumption, the weight ratio of preferred described positive electrode and dispersant is 2: 1 to 3: 2; The weight ratio of described negative material and dispersant is 2: 1 to 4: 3.
The condition of described drying and calendering is known in this field, and promptly described drying can adopt under vacuum condition carries out under 50-160 ℃, and described calendering can be adopted the pressure of 0.5-1.5 MPa.
Because the present invention only relates to the improvement to prior art lithium secondary battery collector, therefore other The Nomenclature Composition and Structure of Complexes to lithium secondary battery has no particular limits.
For example, described positive electrode can be a various positive electrode known in those skilled in the art, generally include the conductive agent that positive active material, adhesive and selectivity contain, described positive active material can be selected from the positive active material of lithium secondary battery routine, as Li
xNi
1-yCoO
2(wherein, 0.9≤x≤1.1,0≤y≤1.0), Li
mMn
2-nB
nO
2(wherein, B is a transition metal, 0.9≤m≤1.1,0≤n≤1.0), Li
1+aM
bMn
2-bO
4(wherein ,-0.1≤a≤0.2,0≤b≤1.0, M is one or more in lithium, boron, magnesium, aluminium, titanium, chromium, iron, cobalt, nickel, copper, zinc, gallium, yttrium, fluorine, iodine, the element sulphur).Preferred described positive active material is one or more in lithium-nickel-cobalt-oxygen thing, lithium and cobalt oxides, the lithium manganese oxide.
Positive electrode of the present invention has no particular limits adhesive, can adopt known in the art all can be used for the adhesive of lithium secondary 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 %.
Positive electrode 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 0-15 weight %, is preferably 0-10 weight %.
Consisting of of negative pole is conventionally known to one of skill in the art, wherein 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 secondary 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 secondary 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 anode sizing agent and 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 positive active material in the slurries be 40-90 weight %, is preferably 50-85 weight %.
Described diaphragm paper 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 diaphragm paper can be the general various diaphragm papers 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
110 gram polyvinylidene fluoride (PVDF) are dissolved in about 1500 gram N-methyl pyrrolidone (NMP) solvents make binder solution, then 3200 gram lithium cobalt oxygen (the KD10 lithium cobalt oxygen of UM) and the acetylene black powder that 30 grams serve as conductive agent are joined in the above-mentioned solution, fully mix and make anode sizing agent; With tensile pulp machine this anode sizing agent being coated to thickness equably is 1.5 millimeters, and tensile strength is 125 newton/square centimeters, and porosity is 92% foamed aluminium two sides, and to make the weight ratio of anode sizing agent and plus plate current-collecting body be 15: 1.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) * 0.5,53 millimeters (length) * 30 millimeter (thick), contain the positive active materials of 1.58 grams on every positive pole.
(2) preparation of negative pole
(Kynoar (PVDF) that serves as adhesive with 40 grams fully mixes electrically conductive 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 equably, makes that the coat side density of negative material is 53 milligrams/square centimeter.Through 125 ℃ of vacuum and heating dryings 1 hour, two rod milling train rolling formations.Cut-parts make the negative pole of millimeter (wide) * 0.1,53 millimeters (length) * 30 millimeter (thick), contain 0.85 graphite that restrains on the every negative pole.
(3) assembling of battery
Positive pole, barrier film, negative pole, barrier film lamination successively included in after good in 55 millimeters * 34 millimeters * 6 millimeters the square aluminum hull.Totally 6 of anodal laminations, the weight ratio of positive electrode and plus plate current-collecting body is 10: 1; 7 of negative pole laminations.
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 7 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.
Anodal and comprise the battery that this is anodal according to the preparation of the method for embodiment 1, different is, selects for use aluminium foil as plus plate current-collecting body, contains the lithium cobalt oxygen of 0.09 gram on every positive pole, and the weight ratio of positive electrode and plus plate current-collecting body is 6: 1.Totally 29 of anodal laminations, 30 of negative pole laminations.
Embodiment 2-5
Embodiment illustrates positive pole provided by the invention and preparation method thereof and comprises the lithium rechargeable battery that this is anodal.
Anodal and comprise the battery that this is anodal according to the preparation of the method for embodiment 1, different is, the electrode material of the material of collector, thickness, tensile strength, porosity, described electrode and the weight ratio of collector are as shown in table 1 below.
Table 1
Wherein, the preparation method of embodiment 4-5 negative pole is electrically conductive graphite (soddif commodity, DAG22) powder 960 grams, the Kynoar (PVDF) that serves as adhesive with 40 grams fully mixes, be dissolved into about 500 grams and serve as in the N-methyl pyrrolidone of solvent, fully mix and make cathode size.With tensile pulp machine with this cathode size equably coating thickness be 1.5 millimeters, tensile strength is 195 newton/square centimeters, porosity is 96% foam copper two sides, and to make the weight ratio of cathode size and collector be 10: 1.Through 125 ℃ of vacuum and heating dryings 1 hour, two rod milling train rolling formations.Cut-parts make the negative pole of millimeter (wide) * 0.3,53 millimeters (length) * 30 millimeter (thick), contain 0.7 graphite that restrains on the every negative pole.
Battery performance test:
(1) battery short circuit rate test:
Whether get the battery that the foregoing description 1-5 and Comparative Examples 1 are made, surveying battery with VC9805A+ type universal instrument (the high company of Shenzhen triumph) has short circuit, and every kind of embodiment or Comparative Examples are measured 1000 batteries respectively, the counting cell short circuit ratio, and the result is as shown in table 2.
Table 2
| Embodiment or Comparative Examples | Embodiment 1 | Comparative Examples 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Short circuit ratio (%) | 1.5 | 10 | 1.6 | 1.8 | 1.2 | 1.1 |
From the result shown in the table 2 as can be seen, the lithium rechargeable battery of the collector of use foam metal provided by the invention, its battery short circuit rate is starkly lower than Comparative Examples 1
(2) battery capacity and weight ratio capacity test
To the battery that the foregoing description 1-6 and Comparative Examples 1 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.
The discharge capacity that records is anodal weight ratio capacity with the ratio of anodal weight.
Measurement result is as shown in table 3.
Table 3
| Embodiment or Comparative Examples | Battery average size (milliampere-hour) | Anodal total weight (gram) | Anodal weight ratio capacity (milliampere-hour/gram) |
| Embodiment 1 | 1380 | 10.2 | 136 |
| Comparative Examples 1 | 1330 | 10.3 | 129 |
| Embodiment 2 | 1370 | 10.1 | 135 |
| Embodiment 3 | 1365 | 10.2 | 134 |
| Embodiment 4 | 1380 | 10.2 | 136 |
| Embodiment 5 | 1383 | 10.2 | 136 |
From the result shown in the table 3 as can be seen, the lithium rechargeable battery of the collector of use foam metal provided by the invention, its battery capacity is higher than Comparative Examples 1 far away.
(3) cycle performance test
To using the cycle performance of the battery that the foregoing description 1-5 and Comparative Examples 1 make, under normal temperature, relative humidity 25-85% environmental condition, measure respectively.Assay method is as follows:
At first, 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 3.0 volts in order to 1000 milliamperes (1C) then, shelved 0.5C constant voltage charge to 4.2 volt, 20 milliamperes of charging cut-off currents again 5 minutes.With electric current constant-current discharge to 3.0 volt of 0.5C, measure the initial capacity that obtains battery discharge then.Circulation repeats to lie prostrate with 1C constant current charge to 4.2; Be discharged to 3.0 volts charge and discharge process again with 1C, write down the loop ends capacity of the 1st time and the 400th time, and be calculated as follows battery capacity surplus ratio and average time attenuation rate:
Capacity surplus ratio=loop ends capacity/initial capacity * 100%.
Average time attenuation rate=(1-capacity surplus ratio)/cycle-index
Measurement result is as shown in table 4.
Table 4
| Embodiment or Comparative Examples | The 1st cyclic discharge capacity (milliampere-hour) | The 400th cyclic discharge capacity (milliampere-hour) | 400 circulation back capacity surplus ratios (%) | Average time attenuation rate (‰) |
| Embodiment 1 | 1389 | 1264 | 91 | 0.2 |
| Embodiment 2 | 1375 | 1224 | 89 | 0.3 |
| Embodiment 3 | 1380 | 1242 | 90 | 0.3 |
| Embodiment 4 | 1387 | 1234 | 89 | 0.3 |
| Embodiment 5 | 1382 | 1244 | 90 | 0.3 |
| Comparative Examples 1 | 1339 | 1071 | 80 | 0.5 |
From the result shown in the table 4 as can be seen: lithium rechargeable battery provided by the invention, compare with the prior art lithium rechargeable battery, cycle performance obviously improves, after the battery of embodiment 1 circulation 400 times, capability retention is 91%, and average time attenuation rate only is 0.2 ‰; And after the battery of Comparative Examples 1 circulation 400 times, capability retention only is 80%, and average time attenuation rate reaches 0.5 ‰.
(4) battery multiplying power discharging test:
To the battery that the foregoing description 1-5 and Comparative Examples 1 make, carry out the test of battery multiplying power discharging 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 270 milliamperes (0.2C) charges to 3.8 volts to mesuring battary, shelved 5 minutes, be discharged to 3.0V in order to 1350 milliamperes (1C) then, shelved again 5 minutes, with 270 milliamperes of (0.2C) constant current charge to 4.2 volts, then with 4.2 volts of constant voltage charges, charging 27 milliamperes of cut-off currents (0.02C).The battery of substituting the bad for the good is discharged with 1C (1350 milliamperes), 2C (2700 milliamperes), 3C (4050 milliamperes) respectively, and discharging into cell voltage is 3.0 volts, the record discharge capacity.
Discharge capacity (milliampere-hour)=discharging current (milliampere) * discharge time (hour)
The discharge capacity of discharge capacity/0.2C of discharge-rate=1C or 2C or 3C * 100%
The results are shown in Table 5.
Table 5
As can be seen from Table 5: lithium rechargeable battery provided by the invention, to compare with the prior art lithium rechargeable battery, heavy-current discharge performance obviously improves.
Claims (10)
1. Laminated Type Lithium Ion Secondary Battery, this battery comprise battery container and are sealed in electrode group and electrolyte in this battery container; Described electrode group comprises positive pole, negative pole and the barrier film between positive pole and negative pole, described positive pole comprises plus plate current-collecting body and the positive electrode that loads on this collector, described negative pole comprises negative current collector and the negative material that loads on this collector, it is characterized in that, described plus plate current-collecting body and/or negative current collector are foam metal, the thickness of described foam metal is the 0.5-3 millimeter, and tensile strength is not less than 120 newton/square centimeters, and porosity is not less than 80%.
2. battery according to claim 1, wherein, the thickness of described foam metal is the 1-2.5 millimeter, and tensile strength is 120-200 newton/square centimeter, and porosity is 90-95%.
3. battery according to claim 1 and 2, wherein, described foam metal is foamed aluminium or foam copper.
4. battery according to claim 1 and 2, wherein, the weight ratio of the weight ratio of described positive electrode and plus plate current-collecting body and/or negative material and negative current collector is greater than 7: 1 to 15: 1.
5. battery according to claim 4, wherein, the weight ratio of the weight ratio of described positive electrode and plus plate current-collecting body and/or negative material and negative current collector is 8: 1 to 10: 1.
6. the preparation method of the described battery of claim 1, this method comprises makes plus plate current-collecting body load positive electrode obtain positive pole, make negative current collector load negative material obtain negative pole, to between positive pole and the negative pole barrier film be set, constitute the electrode group, this electrode group is contained in the battery container, inject electrolyte, then that battery container is airtight, it is characterized in that described plus plate current-collecting body and/or negative current collector are foam metal, the thickness of described foam metal is the 0.5-3 millimeter, tensile strength is not less than 120 newton/square centimeters, and porosity is not less than 80%.
7. method according to claim 6, wherein, the thickness of described foam metal is the 1-2.5 millimeter, and tensile strength is 120-200 newton/square centimeter, and porosity is 90-95%.
8. method according to claim 6, wherein, the described mode of plus plate current-collecting body load positive electrode that makes is coated on the plus plate current-collecting body drying, calendering for the slurry that will contain positive electrode; The described mode of negative current collector load negative material that makes is coated on the negative current collector drying, calendering for the slurry that will contain negative material; The described slurry that contains positive electrode makes the weight ratio of described positive electrode and plus plate current-collecting body and/or negative material and negative current collector at the coated weight on the plus plate current-collecting body and the described coated weight of slurry on negative current collector that contains negative material weight ratio is for greater than 7: 1 to 15: 1.
9. method according to claim 7, wherein, to make the weight ratio of described positive electrode and plus plate current-collecting body and/or the weight ratio of negative material and negative current collector at the coated weight on the plus plate current-collecting body and the described coated weight of slurry on negative current collector that contains negative material be 8: 1 to 10: 1 to the described slurry that contains positive electrode.
10. according to Claim 8 or 9 described methods, wherein, the described slurry that contains positive electrode comprises positive electrode and dispersant, and the described slurry that contains negative material comprises negative material and dispersant, and the weight ratio of described positive electrode and dispersant is 2: 1 to 3: 2; The weight ratio of described negative material and dispersant is 2: 1 to 4: 3.
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