CN101359748B - Lithium-ion secondary cell and manufacturing method therefor - Google Patents
Lithium-ion secondary cell and manufacturing method therefor Download PDFInfo
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- CN101359748B CN101359748B CN2007101300732A CN200710130073A CN101359748B CN 101359748 B CN101359748 B CN 101359748B CN 2007101300732 A CN2007101300732 A CN 2007101300732A CN 200710130073 A CN200710130073 A CN 200710130073A CN 101359748 B CN101359748 B CN 101359748B
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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
Disclosed is a lithium ion secondary battery comprising a pole core and a non-aqueous electrolyte, the pole core and the non-aqueous electrolyte are sealed in a battery shell, the pole core includes an anode, a cathode and a diaphragm, the anode includes a current collector and an anode material loaded on the current collector, and the anode material comprises an anode active substance and an adhesive; the cathode includes a current collector and a cathode material loaded on the current collector, and the cathode material includes a cathode active substance and an adhesive; and the anode material and/or the cathode material are provided with a film respectively, each film comprises an inorganic filler and an adhesive, wherein, each film also contains an active substance, wherein, the active substance in the film on the anode material is an anode active substance, and the active substance in the film on the cathode material is a cathode active substance. The battery made by the method has the advantages of good security and also high capacity and small thickness.
Description
Technical field
The present invention relates to a kind of battery and preparation method thereof, relate in particular to a kind of lithium rechargeable battery and preparation method thereof.
Background technology
Lithium rechargeable battery because of its specific capacity 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 pole piece and nonaqueous electrolytic solution; Described pole piece 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 the conductive agent that positive active material, adhesive and selectivity contain; Described negative pole comprises negative electrode collector and applies negative material on it; Described negative material comprises the conductive agent that negative electrode active material, adhesive and selectivity contain.
The existence of above-mentioned barrier film can prevent from anodal directly contact with negative pole and be short-circuited.But under the situation of some improper use, temperature is too high in the battery, can cause barrier film to dwindle, thereby cause battery short circuit, or the situation that barrier film is pierced takes place, and causes short circuit.In case the battery short circuit, moment produces a large amount of heat, may be explosion caused, thus the user is produced danger.
Along with continuing to increase of lithium ion battery demand, also more and more higher to the performance demands of its various aspects, wherein the fail safe of battery seems particularly important in application.The security performance that how to improve battery is one of emphasis of Study on Li-ion batteries using.
JP 2005-294216A discloses a kind of lithium rechargeable battery, this battery comprises pole piece and nonaqueous electrolytic solution, described pole piece comprises positive pole, negative pole and barrier film, be bonded with perforated membrane on the surface of at least one of described positive pole and negative pole, described perforated membrane is formed by inorganic filler and adhesive, and described inorganic filler can be aluminium oxide, silica, titanium oxide and zirconia etc.
This battery can prevent that electrolyte from directly contacting with active material simultaneously, thereby improve the security performance of battery by be formed with the generation that perforated membrane prevents internal short-circuit of battery at least one surface of positive pole and negative pole.But this battery can make cell thickness increase after forming perforated membrane on the pole piece, can't satisfy the requirement of thin battery, if reduce the purpose of cell thickness by the method that reduces the negative or positive electrode material, then can cause battery capacity to reduce again.Simultaneously, the existence of perforated membrane can cause the increase of the internal resistance of cell, especially under the bigger situation of perforated membrane thickness.Though perhaps can improve above-mentioned situation by the thickness that reduces perforated membrane, for example, the thickness of perforated membrane can be reduced to below 10 microns, improve above-mentioned situation, but in the prior art, general filming below 10 microns is difficult to realize, even can realize also needing high-accuracy equipment, and this can increase the cost of battery production undoubtedly.
Summary of the invention
The objective of the invention is to satisfy the shortcoming that security performance is good, thickness is little, capacity is high simultaneously, provide a kind of security performance good, simultaneously lithium rechargeable battery that the thickness low capacity is high and preparation method thereof in order to overcome lithium rechargeable battery in the prior art.
The invention provides a kind of lithium rechargeable battery, this battery comprises pole piece and nonaqueous electrolytic solution, described pole piece and nonaqueous electrolytic solution are sealed in the battery container, described pole piece comprises positive pole, negative pole and barrier film, described positive pole comprises collector body and the positive electrode that loads on the collector body, and described positive electrode comprises positive active material and adhesive; Described negative pole comprises collector body and the negative material that loads on the collector body, and described negative pole utmost point material comprises negative electrode active material and adhesive; Has rete on described positive electrode and/or the negative material, described rete contains inorganic filler and adhesive, wherein, described rete also contains active material, wherein, active material in the rete on the positive electrode is a positive active material, and the active material in the rete on the negative material is a negative electrode active material.
The present invention also provides the preparation method of lithium rechargeable battery, this method is included in load coating sizing-agent and the dry rete that forms on the collector body of positive active material and adhesive and/or the collector body that load has negative electrode active material and adhesive, then positive pole, negative pole and barrier film are prepared into a pole piece, pole piece and the nonaqueous electrolytic solution that obtains is sealed in the battery case; Described slurry contains inorganic filler, adhesive and solvent, and wherein, described slurry also contains active material, and wherein, the active material that is used for anodal slurry is a positive active material, and the active material that is used for the slurry of negative pole is a negative electrode active material.
The present invention is by forming rete on positive electrode and/or negative material, thereby improved the security performance of battery greatly.And contain active material in the rete of the present invention, therefore, can when satisfying battery safety, make battery have less thickness and higher capacity.For example, when on positive electrode or negative material, being formed with rete, have under the satisfactory situation of close battery capacity and security performance, the minimum thickness of the battery that the present invention makes is all below 5.94 millimeters, minimum reaches 5.66 millimeters, and the thickness of the battery that prior art makes is 6.08 millimeters, therefore, the battery that the present invention makes not only security performance is good, has capacity height, advantage that thickness is little simultaneously.
Embodiment
Lithium rechargeable battery of the present invention comprises pole piece and nonaqueous electrolytic solution, described pole piece and nonaqueous electrolytic solution are sealed in the battery container, described pole piece comprises positive pole, negative pole and barrier film, described positive pole comprises collector body and the positive electrode that loads on the collector body, and described positive electrode comprises positive active material and adhesive; Described negative pole comprises collector body and the negative material that loads on the collector body, and described negative material comprises negative electrode active material and adhesive; Has rete on described positive electrode and/or the negative material, described rete contains inorganic filler and adhesive, wherein, described rete also contains active material, wherein, active material in the rete on the positive electrode is a positive active material, and the active material in the rete on the negative material is a negative electrode active material.
In the rete on the positive electrode of the present invention, the weight of relative positive active material, the content of inorganic filler is 40-260 weight %, the content of adhesive is 0.1-15 weight %; In the rete on the described negative material, the weight of relative negative electrode active material, the content of inorganic filler is 40-260 weight %, the content of adhesive is 0.1-15 weight %.
Under the preferable case, in the rete on the described positive electrode, the weight of relative positive active material, the content of inorganic filler is 40-200 weight %, the content of adhesive is 1-10 weight %; In the rete on the described negative material, the weight of relative negative electrode active material, the content of inorganic filler is 40-200 weight %, the content of adhesive is 1-10 weight %.
The thickness of rete of the present invention can be the 5-30 micron, and thicknesses of layers is too small, and difficulty strengthens on the implementation, certainly will cause the raising of production cost, thicknesses of layers is excessive, can cause the increase of cell thickness, therefore under the preferable case, the thickness of described rete is the 10-25 micron.
Inorganic filler of the present invention is conventionally known to one of skill in the art.For example, can be in aluminium oxide, silica, titanium oxide and the zirconia one or more.Be preferably in aluminium oxide, titanium oxide and the silica one or more.The mean particle diameter of described inorganic filler can be the 0.01-2 micron, is preferably the 0.1-1 micron.
Positive active material of the present invention and negative electrode active material are conventionally known to one of skill in the art.Described positive active material can be a kind of or its mixture: the Li in the following material
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); Be preferably in lithium cobalt oxygen, lithium nickel oxygen, lithium manganese oxygen, lithium-nickel-cobalt-oxygen, Li-Ni-Mn-O and the Li-Ni-Mn-Co-O one or more.
Described negative electrode active material can be one or more in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal, the silicon alloy, is preferably native graphite and/or Delanium.
The adhesive of the present invention in positive electrode is the conventional adhesive that is used for lithium ion cell positive that uses.For example, adhesive in the described positive electrode can be one or more in fluorine resin, acrylic polymer, amine polymer and the polyolefin compound, is preferably in polyvinylidene fluoride, polytetrafluoroethylene, vinylidene difluoride-hexafluoropropylene copolymer, polyamidoimide and the butadiene-styrene rubber one or more.Adhesive consumption in the positive electrode is conventionally known to one of skill in the art.For example, in positive electrode, the weight of relative positive active material, the content of described adhesive is 0.1-10 weight %, is preferably 1-5 weight %.Adhesive in the rete on the positive electrode also can be one or more in fluorine resin, acrylic polymer, amine polymer and the polyolefin compound, be preferably in polyvinylidene fluoride, polytetrafluoroethylene, vinylidene difluoride-hexafluoropropylene copolymer, polyamidoimide and the butadiene-styrene rubber one or more, and with the adhesive in the positive electrode can be identical or different.
The adhesive of the present invention in negative material is the conventional adhesive that is used for lithium ion battery negative that uses.For example, adhesive in the described negative material can be one or more in fluorine resin, acrylic polymer, amine polymer and the polyolefin compound, is preferably in polyvinylidene fluoride, polytetrafluoroethylene, vinylidene difluoride-hexafluoropropylene copolymer, polyamidoimide and the butadiene-styrene rubber one or more.Adhesive consumption in the negative material is conventionally known to one of skill in the art.For example, in negative material, the weight of relative negative electrode active material, the content of described adhesive is 0.1-10 weight %, is preferably 1-5 weight %.In addition, adhesive in the rete on the negative material also can be one or more in fluorine resin, acrylic polymer, amine polymer and the polyolefin compound, be preferably in polyvinylidene fluoride, polytetrafluoroethylene, vinylidene difluoride-hexafluoropropylene copolymer, polyamidoimide and the butadiene-styrene rubber one or more, and with the adhesive in the negative material can be identical or different.
In addition, can also contain the adhesive auxiliary agent in the described negative material, described adhesive auxiliary agent is conventionally known to one of skill in the art.For example, described adhesive auxiliary agent can be one or more in carboxymethyl cellulose (CMC), hydroxypropyl methylcellulose (HPMC), methylcellulose (MC), hydroxypropyl cellulose (HPC) and the carboxymethyl hydroxyethyl cellulose (CMHEC).In general, the content of described adhesive auxiliary agent is the 0.1-5 weight % of negative electrode active material weight.In addition, also can contain described adhesive auxiliary agent in the rete on described negative material, the content of described adhesive auxiliary agent is the 0.1-5 weight % of negative electrode active material weight in the rete.
The collector body of described positive pole can be a positive electrode collector conventional in the lithium ion battery, and as aluminium foil, Copper Foil, nickel plated steel strip, the present invention selects for use aluminium foil to make collector body.
The collector body of described negative pole can be a negative electrode collector conventional in the lithium ion battery, as stamped metal, metal forming, net metal, foamed metal, uses Copper Foil as negative electrode collector in specific embodiments of the present invention.
Described barrier film has electrical insulation capability and liquid retainability energy, and the kind of barrier film and character are conventionally known to one of skill in the art.Described barrier film can be selected from various barrier films used in the lithium ion battery, as polyolefin micro porous polyolefin membrane, polyethylene felt, glass mat or ultra-fine fibre glass paper.
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 1.5-4.9g/Ah, the concentration of electrolyte be generally 0.5-2.9 rub/liter.
The preparation method of lithium rechargeable battery of the present invention is included in load coating sizing-agent and the dry rete that forms on the collector body of positive active material and adhesive and/or the collector body that load has negative electrode active material and adhesive, then positive pole, negative pole and barrier film are prepared into a pole piece, pole piece and the nonaqueous electrolytic solution that obtains is sealed in the battery case; Described slurry contains inorganic filler, adhesive and solvent, and wherein, described slurry also contains active material, and wherein, the active material that is used for anodal slurry is a positive active material, and the active material that is used for the slurry of negative pole is a negative electrode active material.
The described slurry that is used for positive pole, the weight of relative positive active material, the consumption of inorganic filler is 40-260 weight %, and adhesive consumption is 0.1-15 weight %, and the consumption of solvent is 100-400 weight %; The described slurry that is used for negative pole, the weight of relative negative electrode active material, the consumption of inorganic filler is 40-260 weight %, and adhesive consumption is 0.1-15 weight %, and the consumption of solvent is 100-400 weight %.
Under the preferable case, the described slurry that is used for positive pole, the weight of relative positive active material, the consumption of inorganic filler is 40-200 weight %, and adhesive consumption is 1-10 weight %, and the consumption of solvent is 100-300 weight %; The described slurry that is used for negative pole, the weight of relative negative electrode active material, the consumption of inorganic filler is 40-200 weight %, and adhesive consumption is 1-10 weight %, and the consumption of solvent is 100-300 weight %.
As long as described slurry is with active material, inorganic filler, adhesive and solvent evenly.In order to make active material and inorganic filler fully disperse in slurry, under the preferable case, described slurry obtains mixture by earlier active material being mixed with inorganic filler, and then this mixture is joined in the solvent.The addition sequence of described adhesive without limits, described adhesive can add simultaneously with said mixture, also can join earlier and dissolve formation solution in the solvent.
The coating process of described slurry can be coated with by the coating process of routine, can be identical with the coating process of anode sizing agent in the common anode preparation.As long as the thickness of described slurry coating makes the thickness of the rete that obtains after the drying be the 5-30 micron, be preferably the 10-25 micron.In addition, as long as described drying for example can get final product under 70-200 ℃ except that desolvating in 1-20 minute in heating.In addition, after drying, can also roll.The method of described calendering is conventionally known to one of skill in the art.
In addition, can also add described adhesive auxiliary agent at the described slurry that is used for negative pole, the consumption of described adhesive auxiliary agent is the 0.1-5 weight % of negative electrode active material weight in the rete.
The kind of described active material, inorganic filler, adhesive and adhesive auxiliary agent is narrated in the above, repeats no more herein.
In addition, the solvent that is used for anodal slurry can be all kinds of solvents that uses in the conventional lithium ion cell positive preparation.For example, can be in N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and the water one or more.
The solvent that is used for the slurry of negative pole can be all kinds of solvents that uses in the conventional lithium ion battery negative preparation.For example, can be in N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and the water one or more.
Battery of the present invention has the rete except described positive pole and/or negative pole, and other structure and preparation method are conventionally known to one of skill in the art.
With positive active material and adhesive load can be the method that adopts in the conventional lithium ion cell positive preparation to the method on the collector body.For example, positive active material and adhesive can be dissolved into the anodal slurries of formation in the solvent, should be applied on the collector body and drying by the positive pole slurries then, roll or do not roll.In anodal slurries, the weight of relative positive active material, described adhesive consumption is 0.5-8 weight %, is preferably 1-5 weight %.The consumption of described solvent is 30-90 weight %, is preferably 35-85 weight %.
With negative electrode active material and adhesive load can be the method that adopts in the conventional lithium ion battery negative preparation to the method on the collector body.For example, negative electrode active material and adhesive can be dissolved into formation negative pole slurries in the solvent, then these negative pole slurries be applied on the collector body and drying, roll or do not roll.In the negative pole slurries, the weight of relative negative electrode active material, described adhesive consumption is 0.01-8 weight %, is preferably 0.02-5 weight %, the consumption of described solvent is 30-90 weight %, is preferably 35-85 weight %.In addition, can also contain the adhesive auxiliary agent in the described negative pole slurries, the content of described adhesive auxiliary agent is the 0.1-5 weight % of the negative electrode active material weight in the negative pole slurries.The kind of described adhesive auxiliary agent is narrated in the above, repeats no more herein.
Can also add conductive agent in the described anodal slurries, described conductive agent can be the anodal conductive agent of this area routine, and described conductive agent for example can be at least a in acetylene black, conductive carbon black and the electrically conductive graphite.In anodal slurries, be benchmark with the weight of positive active material, the consumption of described conductive agent is 1-15 weight %, is preferably 2-10 weight %.
Can also add conductive agent in the described negative pole slurries, described conductive agent can be the cathode conductive agent of this area routine, such as in carbon black, nickel powder and the copper powder one or more.In the negative pole slurries, be benchmark with the weight of negative electrode active material, the consumption of described conductive agent is 0-15 weight %, is preferably 2-10 weight %.
Described barrier film is arranged between positive pole and the negative pole, and the kind of described barrier film is narrated in front.
To the present invention be described in more detail by embodiment below.
Embodiment 1
This embodiment explanation the invention provides lithium ion battery and the preparation method.
(1) Zheng Ji preparation
With 10 kilograms of positive active material LiCoO
2, 300 gram polyvinylidene fluoride, 400 gram conductive agent acetylene blacks join in 5 kilograms of N-methyl pyrrolidones, in de-airing mixer, stir then and form uniform anodal slurries.These slurries are coated on the aluminium foil equably, then 150 ℃ of positive plates that descend oven dry, roll-in to obtain being formed with positive electrode.
With 300 gram positive active material LiCoO
2With 700 gram aluminium oxide (producers: the river that jumps, Shanghai, mean particle diameter is 0.5 micron) mix and obtain mixture, this mixture is added in the 500 gram N-methyl pyrrolidones, add 30 gram polyvinylidene fluoride then, obtain being used for anodal slurry after mixing, this is used for anodal slurry is applied to above-mentioned positive plate, then 150 ℃ of oven dry down, and roll-in, formation thickness is 20 microns rete, then, cut to make and be of a size of 540 * 43.5 millimeters positive pole, contain 5.8 gram positive active material LiCoO in this positive pole altogether
2
(2) preparation of negative pole
10 kilograms of negative electrode active material native graphites, 400 gram adhesive polytetrafluoroethylene (PTFE)s, 400 gram conductive agent carbon blacks are joined in 4 kilograms of methyl-sulfoxides (DMSO), in de-airing mixer, stir then and form negative pole slurries stable, homogeneous.These negative pole slurries are coated on the Copper Foil equably, obtain negative plate through 120 ℃ of oven dry, rollings.
With 300 gram negative electrode active material electrographites (producer: clear and chemical industry) with 700 gram aluminium oxide (producer: the river that jumps, Shanghai, mean particle diameter is 0.5 micron) mix and obtain mixture, this mixture is added in the 900 gram N-methyl pyrrolidones, add 30 gram polyvinylidene fluoride then, obtain being used for the slurry of negative pole after mixing, this slurry that is used for negative pole is applied to above-mentioned negative plate, then 150 ℃ of oven dry down, and roll-in, formation thickness is 20 microns rete, cut then to make and be of a size of 355 millimeters * 43 millimeters negative pole, contain 2.7 gram negative electrode active material electrographites in this negative pole.
(3) assembling of battery
With LiPF
6Be configured to LiPF with ethylene carbonate (EC) and diethyl carbonate (DEC)
6Concentration is the solution (wherein, the volume ratio of EC and DEC is 1: 1) of 1.0 mol, obtains nonaqueous electrolytic solution.The negative pole that positive pole, membrane layer, (2) that (1) is obtained obtain is successively with the stacked electrode group that is wound into scroll of up-coiler, the electrode group that obtains is put into the battery case of an end opening, and inject above-mentioned nonaqueous electrolytic solution with the amount of 3.8g/Ah, make lithium ion battery A1 after the sealing.
Embodiment 2
Method according to embodiment 1 prepares battery, and different is only to form rete on positive pole.Contain 2.7 gram negative electrode active material electrographites on the described negative pole.Finally obtain lithium ion battery A2.
Embodiment 3
Method according to embodiment 1 prepares battery, and different is only to form rete on negative pole.Contain 5.8 gram positive active material LiCoO on the described positive pole
2Finally obtain lithium ion battery A3.
Embodiment 4
Method according to embodiment 3 prepares battery, different is, the slurry that is used on negative material forming rete is with 400 gram negative electrode active material electrographites (producer: clear and chemical industry) with 600 gram aluminium oxide (producer: the river that jumps, Shanghai, 0.5 micron of particle diameter) mixes and obtain mixture, this mixture is joined in the 800 gram water, add 20 gram butadiene-styrene rubber and 20 gram carboxymethyl celluloses then and evenly mix and obtain.The thickness of the rete that forms is 18 microns.Contain 2.7 gram negative electrode active material electrographites on the described negative pole.Finally obtain lithium ion battery A4.
Embodiment 5
Method according to embodiment 3 prepares battery, different is, the slurry that is used on negative pole forming rete is with 500 gram negative electrode active material electrographites (producer: Changsha Hai Rong) with 500 gram titanium oxide (producer: the river that jumps, Shanghai, 0.8 micron of particle diameter) mixes and obtain mixture, this mixture is joined in the 900 gram N-methyl pyrrolidones, add 30 gram polyvinylidene fluoride then, mix and obtain.The thickness of the rete that forms is 17 microns.Contain 2.7 gram negative electrode active material electrographites on the described negative pole.Finally obtain lithium ion battery A5.
Embodiment 6
Method according to embodiment 3 prepares battery, different is, the slurry that is used to form rete is 600 a gram negative electrode active material carbon fibers (producer: Shanghai China fir China fir) with 400 gram zirconias (producer: the river that jumps, Shanghai just, 0.6 micron of particle diameter) mixes and obtain mixture, this mixture is joined in the 900 gram N-methyl pyrrolidones, add 30 gram polyvinylidene fluoride then, mix and obtain.The thickness of the rete that forms is 16 microns.Contain 2.7 gram negative electrode active material electrographites on the described negative pole.Finally obtain lithium ion battery A6.
Embodiment 7
Method according to embodiment 3 prepares battery, different is, the slurry that is used to form rete is with 700 gram negative electrode active materials organic cracking carbon (producer: Shanghai China fir China fir) with 300 gram silica (producer: the river that jumps, Shanghai, 0.5 micron of particle diameter) mixes and obtain mixture, this mixture is added in the 900 gram N-methyl pyrrolidones, add 30 gram polyvinylidene fluoride then, mix and obtain.The thickness of the rete that forms is 14 microns.Contain 2.7 gram negative electrode active material electrographites on the described negative pole.Finally obtain lithium ion battery A7.
Embodiment 8
Method according to embodiment 2 prepares battery, and different is, is used to form positive electrode and is used to form in the slurry of rete, and described positive active material is lithium manganese oxygen (LiMn
2O
4).Finally obtain lithium ion battery A8.
Comparative Examples 1
Method according to embodiment 3 prepares battery, and different is not form rete on the negative pole.Contain 2.7 gram negative electrode active material electrographites on the described negative pole.Finally obtain lithium ion battery D1.
Comparative Examples 2
Method according to embodiment 3 prepares battery, and different is, is used to form in the slurry of rete not add the negative electrode active material electrographite.Contain 2.7 gram negative electrode active material electrographites on the described negative pole.Finally obtain lithium ion battery D2.
Embodiment 9-16
These embodiment illustrate the performance of the battery A1-A8 that the present invention makes.
(1) cell thickness is measured
Measure the thickness of the battery A1-A8 that makes respectively with vernier caliper, the result is as shown in table 1.
(2) test of battery capacity
Use BS-9300R secondary cell device for detecting performance respectively the above-mentioned battery A1-A8 that makes to be carried out the mensuration of battery capacity.Test environment is 25 ℃, relative humidity 30%, and assay method is as follows:
To 4.2V, stop electric current 100mA with the 1C current charges, then with the 0.5C current discharge to 3.0V, the record discharge capacity value, unit is a milliampere-hour.The result is as shown in table 1.
(3) acupuncture experiment
Respectively battery A1-A8 is carried out following experiment:
With battery with the 1C current charges to 4.2V, stop electric current 100mA, in safety cage, pierce through battery with the speed of 5mm/s then with the iron nail of φ=2.5mm, with the temperature of the TES1310 digital display thermometer record battery surface after a minute, when the temperature of battery surface is reduced to below 40 ℃, battery is blasted or back on fire finishes to test.Thereby obtain the maximum temperature of battery surface.The result is as shown in table 1.
Comparative Examples 3-4
Method according to embodiment 9 is carried out performance test to battery D1 and the D2 that Comparative Examples 1-2 makes.The result is as shown in table 1.
Table 1
| The battery source | The battery numbering | Cell thickness (mm) | Battery capacity (mAh) | The battery surface maximum temperature (℃) |
| Embodiment 1 | A1 | 6.22 | 1072 | 56 |
| Embodiment 2 | A2 | 5.94 | 1068 | 59 |
| The battery source | The battery numbering | Cell thickness (mm) | Battery capacity (mAh) | The battery surface maximum temperature (℃) |
| Embodiment 3 | A3 | 5.94 | 1070 | 59 |
| Embodiment 4 | A4 | 5.87 | 1074 | 63 |
| Embodiment 5 | A5 | 5.79 | 1068 | 68 |
| Embodiment 6 | A6 | 5.71 | 1068 | 73 |
| Embodiment 7 | A7 | 5.66 | 1070 | 77 |
| Embodiment 8 | A8 | 5.93 | 1070 | 60 |
| Comparative Examples 1 | D1 | 5.53 | 1073 | 567 |
| Comparative Examples 2 | D2 | 6.08 | 1069 | 59 |
As can be seen from Table 1, battery A1 is that the both positive and negative polarity surface all has rete, and the maximum temperature of battery surface is minimum after the acupuncture experiment; The both positive and negative polarity surface of battery D1 does not all have rete, and battery is blasted when carrying out the acupuncture experiment; Battery D2 has rete on the negative material of negative pole, but do not contain negative electrode active material in this rete, the maximum temperature of this battery D2 battery surface in the acupuncture experiment is lower, but battery D2 is in order to obtain higher capacity, make cell thickness obviously increase, even with the THICKNESS CONTROL of battery D2 in small range, in order to guarantee the security performance of battery, thickness that certainly will be by reducing the cell negative electrode material layer is to achieve the goal, but can cause battery capacity to reduce so undoubtedly, therefore can't satisfy high power capacity simultaneously, high safety performance, and the requirement that thickness is little; Battery A2-A8 films at an electrode surface, and along with the reduction of inorganic filler content in filming, cell thickness is more and more thinner, though acupuncture experiment back battery surface maximum temperature raises, all below 80 ℃, can satisfy the requirement of common battery security.
Claims (10)
1. lithium rechargeable battery, this battery comprises pole piece and nonaqueous electrolytic solution, described pole piece and nonaqueous electrolytic solution are sealed in the battery container, described pole piece comprises positive pole, negative pole and barrier film, described positive pole comprises collector body and the positive electrode that loads on the collector body, and described positive electrode comprises positive active material and adhesive; Described negative pole comprises collector body and the negative material that loads on the collector body, and described negative material comprises negative electrode active material and adhesive; Has rete on described positive electrode and/or the negative material, described rete contains inorganic filler and adhesive, it is characterized in that, described rete also contains active material, wherein, active material in the rete on the positive electrode is a positive active material, and the active material in the rete on the negative material is a negative electrode active material.
2. battery according to claim 1, wherein, in the rete on the described positive electrode, the weight of relative positive active material, the content of inorganic filler is 40-260 weight %, the content of adhesive is 0.1-15 weight %; In the rete on the described negative material, the weight of relative negative electrode active material, the content of inorganic filler is 40-260 weight %, the content of adhesive is 0.1-15 weight %.
3. battery according to claim 2, wherein, in the rete on the described positive electrode, the weight of relative positive active material, the content of inorganic filler is 40-200 weight %, the content of adhesive is 1-10 weight %; In the rete on the described negative material, the weight of relative negative electrode active material, the content of inorganic filler is 40-200 weight %, the content of adhesive is 1-10 weight %.
4. battery according to claim 1, wherein, the thickness of described rete is the 10-25 micron.
5. battery according to claim 1, wherein, described inorganic filler is one or more in aluminium oxide, silica, titanium oxide and the zirconia; Adhesive in the described positive pole is one or more in polyvinylidene fluoride, polytetrafluoroethylene, vinylidene difluoride-hexafluoropropylene copolymer, polyamidoimide and the butadiene-styrene rubber; Adhesive in the described negative pole is one or more in polyvinylidene fluoride, polytetrafluoroethylene, vinylidene difluoride-hexafluoropropylene copolymer, polyamidoimide and the butadiene-styrene rubber.
6. battery according to claim 5, wherein, the mean particle diameter of described inorganic filler is the 0.1-2 micron.
7. battery according to claim 1, wherein, described positive active material is one or more in lithium cobalt oxygen, lithium nickel oxygen, lithium manganese oxygen, lithium-nickel-cobalt-oxygen, Li-Ni-Mn-O and the Li-Ni-Mn-Co-O, and described negative electrode active material is one or more in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal and the silicon alloy.
8. the preparation method of the described lithium rechargeable battery of claim 1, this method is included in load coating sizing-agent and the dry rete that forms on the collector body of positive active material and adhesive and/or the collector body that load has negative electrode active material and adhesive, then positive pole, negative pole and barrier film are prepared into a pole piece, pole piece and the nonaqueous electrolytic solution that obtains is sealed in the battery case; Described slurry contains inorganic filler, adhesive and solvent, it is characterized in that, described slurry also contains active material, and wherein, the active material that is used for anodal slurry is a positive active material, and the active material that is used for the slurry of negative pole is a negative electrode active material.
9. method according to claim 8, wherein, the described slurry that is used for positive pole, the weight of relative positive active material, the consumption of inorganic filler is 40-260 weight %, and adhesive consumption is 0.1-15 weight %, and the consumption of solvent is 100-400 weight %; The described slurry that is used for negative pole, the weight of relative negative electrode active material, the consumption of inorganic filler is 40-260 weight %, and adhesive consumption is 0.1-15 weight %, and the consumption of solvent is 100-400 weight %.
10. method according to claim 8, wherein, the thickness of described rete is the 10-25 micron.
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| CN102074732A (en) * | 2010-12-25 | 2011-05-25 | 东莞市良源电池科技有限公司 | Lithium ion battery provided with high molecular weight adhesive |
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| CN1969411A (en) * | 2004-04-19 | 2007-05-23 | 松下电器产业株式会社 | Lithium-ion secondary battery and its manufacturing method |
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| CN1969411A (en) * | 2004-04-19 | 2007-05-23 | 松下电器产业株式会社 | Lithium-ion secondary battery and its manufacturing method |
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