CN100470887C - Battery anode, lithium-ion battery therewith and their production - Google Patents
Battery anode, lithium-ion battery therewith and their production Download PDFInfo
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- CN100470887C CN100470887C CNB2005101301030A CN200510130103A CN100470887C CN 100470887 C CN100470887 C CN 100470887C CN B2005101301030 A CNB2005101301030 A CN B2005101301030A CN 200510130103 A CN200510130103 A CN 200510130103A CN 100470887 C CN100470887 C CN 100470887C
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Abstract
The invention is concerned with the lithium ion battery positive electrode, includes the conductive base body, and the anode material smearing and / or filling on the conductive base body, the anode material includes the anode active material, the conductive liquid and the bond, the anode active material is LiNixCoyMn1-x-yO2, 0.1<=x<=0.5 and 0.1<= y<=0.5 in the formula, the characteristic is: the dressing density of the anode active material is 3.4-3.8 grams / cube centimeters. The invention is higher capability and higher space using rate.
Description
Technical field
The invention relates to a kind of anode and use this anodal battery and their preparation method, specifically, the invention relates to a kind of anode and use this anodal lithium ion battery and their preparation method.
Background technology
Lithium ion battery is as a kind of chemical power source, refers to respectively the secondary cell that constitutes as both positive and negative polarity with two compounds that can reversibly embed with the removal lithium embedded ion.When battery charge, lithium ion takes off embedding from positive pole, in negative pole, embed, otherwise during discharge.Lithium ion battery mainly comprises electrode group and nonaqueous electrolytic solution, described electrode group and nonaqueous electrolytic solution are sealed in the battery container, described electrode group comprises battery electrode and barrier film, described battery electrode comprises positive pole and negative pole, described positive pole comprises conducting base and coating and/or is filled in positive electrode on the conducting base that described positive electrode comprises positive active material, conductive agent and adhesive.The preparation method of anode comprises that the slurry that will contain positive electrode and solvent applies and/or is filled on the conducting base, and drying is rolled or do not rolled.
Positive electrode active materials in the anode material for lithium-ion batteries commonly used at present mainly contains lithium cobalt oxygen (LiCoO
2), lithium nickel oxygen (LiNiO
2) and lithium manganese oxygen (LiMn
2O
4).
LiCoO
2In cobalt belong to rare metal, the reserves in the earth's crust are few, thereby cost an arm and a leg, simultaneously cobalt is poisonous, and environment is had destruction; And LiCoO
2When overcharging, just charging voltage is higher than under the situation of 4.2V, and recurring structure destroys easily, and thermal stability is relatively poor, causes the circulation image variation of battery, so charging voltage low (higher limit of charging voltage is 4.2V); In addition, LiCoO
2Reversible capacity be about 140mAh/g, not high relatively.
LiNiO
2And LiMn
2O
4Price lower, environment is not polluted, but LiNiO
2The layer structure poor stability, and stoichiometric LiNiO
2Be difficult to synthesize, under the high temperature synthesis condition, can take place again the mixing occupy-place of lithium nickel at low temperatures.By the control of accurate condition (in the oxygen atmosphere under 750 ℃ of temperature roast 24 hours), can synthesize LiNiO
2It has higher initial specific capacity (initial charge capacity reaches 200mAh/g), but cycle performance is poor especially.
LiMn
2O
4Synthetic simple, but specific capacity little (120mAh/g), and since the manganese ion of high price under higher temperature, be easy to react LiMn with electrolyte
2O
4High temperature (50 ℃) cycle performance extreme difference.
Therefore, Many researchers has been placed on LiNiCoMnO with research emphasis recently
2On the ternary system, for example CN1614801A discloses the novel lithium ion battery multi-element composite positive pole material of a class, and the composition expression formula of this positive electrode is: LiCo
xNi
yMn
1-x-yO
2, 0.1≤x in the formula≤0.6,0.1≤y≤0.5, x+y≤1.This class composite positive pole has charging voltage height, specific capacity height and the good advantage of thermal stability.Though this class new material has a lot of incomparable advantages of other material, when being applied to battery, the capacity of battery but can not get promoting, if the raising battery capacity, thereby then cell thickness can increase the space availability ratio reduction that causes inside battery.
Summary of the invention
Goal of the invention of the present invention is to overcome existing use LiNiCoMnO
2The shortcoming that the capacity of the lithium ion battery of composite material is not high, the inside battery space availability ratio is lower provides a kind of and can improve the anode of battery capacity and inside battery space availability ratio simultaneously and use this anodal lithium ion battery.
Another object of the present invention provides the preparation method of anode and uses the preparation method of this anodal lithium ion battery.
The present inventor finds, is adopting LiNiCoMnO
2When composite material prepares anode as positive active material, the dressing density of positive electrode can influence the space availability ratio of the capacity and the inside battery of battery, in order to make full use of the space of inside battery, improve the space availability ratio of battery, must improve the dressing density of positive plate, but be subjected to LiNiC0MnO
2The influence of the tap density of composite material, if dressing density is too high, then pole piece is thinner, can cause positive plate to become very crisp, pole piece ruptures in the coiling Battery Pole Core, and battery capacity is got a promotion, even makes the preparation of battery to finish.In addition, because LiNi
xCo
yMn
1-x-yO
2Electric conductivity bad, when dressing density was too big, the embedding ability of taking off of lithium ion was suppressed, electrolyte can't soak into positive pole fully, the charge and discharge performance of battery is affected, battery capacity is also received influence.If dressing density is too little, then cell thickness can increase, and makes that the space waste of battery is serious, and space availability ratio reduces.
The invention provides a kind of lithium ion cell positive, this positive pole comprises conducting base and coating and/or is filled in positive electrode on the conducting base, and described positive electrode comprises positive active material, conductive agent and adhesive, and described positive active material is LiNi
xCo
yMn
1-x-yO
2, in the formula, 0.1≤x≤0.5,0.1≤y≤0.5, wherein, the dressing density of described positive electrode is the 3.4-3.8 gram per centimeter
3
The invention provides a kind of preparation method of lithium ion cell positive, this method comprises that the slurry that will contain positive electrode and solvent applies and/or is filled on the conducting base, dry, calendering, described positive electrode comprises positive active material, conductive agent and adhesive, and described positive active material is LiNi
xCo
yMn
1-x-yO
2, in the formula, 0.1≤x≤0.5,0.1≤y≤0.5, wherein, it is the 3.4-3.8 gram per centimeter that the pressure of described calendering makes the dressing density of positive electrode
3
The invention provides a kind of lithium ion battery, this lithium ion battery comprises electrode group and nonaqueous electrolytic solution, described electrode group and nonaqueous electrolytic solution are sealed in the battery container, described electrode group comprises positive pole, negative pole and barrier film, described positive pole comprises conducting base and coating and/or is filled in positive electrode on the conducting base, described positive electrode comprises positive active material, conductive agent and adhesive, and described positive active material is LiNi
xCo
yMn
1-x-yO
2, in the formula, 0.1≤x≤0.5,0.1≤y≤0.5, wherein, described positive pole just very provided by the invention.
The invention provides a kind of preparation method of lithium ion battery, this method comprises positive pole and the negative pole for preparing battery, and positive pole, negative pole and barrier film are prepared into an electrode group, the electrode group and the electrolyte that obtain are sealed in the battery case, the preparation method of described positive pole comprises that the slurry that will contain positive electrode and solvent applies and/or is filled on the conducting base, drying, calendering, described positive electrode comprises positive active material, conductive agent and adhesive, and described positive active material is LiNi
xCo
yMn
1-x-yO
2, in the formula, 0.1≤x≤0.5,0.1≤y≤0.5, wherein, described positive pole just very provided by the invention.
Lithium ion battery provided by the invention is controlled at the 3.4-3.8 gram per centimeter by the dressing density with described positive electrode
3Between and improved LiNiCoMnO well
2Some defectives of composite material itself, can well utilize the advantage of this material again, thereby guaranteed that the battery capacity that obtains with this material preparation and the space availability ratio of battery are improved simultaneously, in addition, compared with prior art, with the positive active material of identical amount, obtain higher battery capacity, reduced raw-material cost again, in addition, the security performance and the discharge performance of battery also are guaranteed simultaneously.
Embodiment
According to lithium ion cell positive provided by the invention, the dressing density of described positive electrode refers to the weight of positive electrode in unit volume, described positive electrode comprises positive active material, conductive agent and adhesive, therefore, the dressing density of described positive electrode is the volume of the weight/positive electrode of positive electrode, the volume of described positive electrode=(pole piece thickness-conducting base thickness) * positive electrode length * positive electrode width.Under the preferable case, the dressing density of described positive electrode is the 3.5-3.7 gram per centimeter
3
According to lithium ion cell positive provided by the invention, described positive active material is LiNi
xCo
yMn
1-x-yO
2, in the formula, 0.1≤x≤0.5,0.1≤y≤0.5, this positive active material has been conventionally known to one of skill in the art, can be commercially available, also can be by existing method preparation, for example disclosed method among the CN1614801A.
Described anodal conductive agent can adopt the anodal conductive agent of this area routine, such as in conductive carbon black, acetylene black, the electrically conductive graphite one or more.Total weight with positive active material is a benchmark, and the content of described conductive agent is 1-15 weight %, is preferably 2-10 weight %.
The kind of described adhesive and content are conventionally known to one of skill in the art, for example one or more in fluorine resin and polyolefin compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), the butadiene-styrene rubber (SBR).In general, according to the difference of adhesive therefor kind, be benchmark with the weight of positive active material, the content of adhesive is 0.01-8 weight %, is preferably 1-5 weight %.
The kind of described anodal conducting base has been conventionally known to one of skill in the art, for example can be selected from aluminium foil, Copper Foil, Punching steel strip.In the specific embodiment of the present invention, use aluminium foil as anodal conducting base.
The preparation method of anode provided by the invention comprises that the slurry that will contain positive electrode and solvent applies and/or is filled on the conducting base, dry, calendering, described positive electrode comprises positive active material, conductive agent and adhesive, described positive active material is LiNi
xCo
yMn
1-x-yO
2, in the formula, 0.1≤x≤0.5,0.1≤y≤0.5, wherein, it is the 3.4-3.8 gram per centimeter that the pressure of described calendering makes the dressing density of positive electrode
3
Influence the pressure of the factor of positive electrode dressing density most critical for calendering, in order to reach dressing density of the present invention, in general, the pressure of described calendering is controlled at the 1.6-2.4 MPa.In addition, the tap density of positive active material also is a factor that influences anode dressing density, though under above-mentioned calendering pressure, the positive active material of different tap densities all can use, but under the preferable case, the tap density of described positive active material is the 1.5-2.5 gram per centimeter
3, be preferably the 1.6-2.4 gram per centimeter
3Between.The tap density of described positive active material is under abundant filling condition, the weight of described positive active material in unit volume.The assay method of described tap density can adopt standard determination method known in those skilled in the art to record.
The kind of solvent, positive active material, conductive agent and adhesive and consumption are conventionally known to one of skill in the art in the described slurry.In general, be benchmark with the weight of positive active material, the content of described solvent is 40-90 weight %, is preferably 50-85 weight %.The content of described positive active material, conductive agent and adhesive is the 40-85 weight % of anode sizing agent total weight, is preferably 60-75 weight %.Described solvent can be selected from one or more in N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), the oxolane (THF); The consumption of solvent can make described pastel have viscosity and flowability, can be coated on the described conducting base to get final product.
Lithium ion battery provided by the invention comprises electrode group and nonaqueous electrolytic solution, and described electrode group and nonaqueous electrolytic solution are sealed in the battery container, and described electrode group comprises positive pole, negative pole and barrier film.Except using, can use conventional negative pole, barrier film, nonaqueous electrolytic solution by the positive pole provided by the invention.
Because the positive active material of lithium ion battery provided by the invention is LiNi
xCo
yMn
1-x-yO
2, in the formula, 0.1≤x≤0.5,0.1≤y≤0.5, therefore the charging voltage of lithium ion battery provided by the invention is more than or equal to 4.3 volts.
Described barrier film is arranged between positive pole and the negative pole, has electrical insulation capability and liquid retainability energy.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.The position of described barrier film, character and kind are conventionally known to one of skill in the art.
Consisting of of described negative pole is conventionally known to one of skill in the art.In general, negative pole comprises conducting base and coating and/or is filled in negative material on the conducting base that described negative material comprises negative electrode active material and negative pole adhesive.
Described negative electrode active material is not particularly limited, can use embedding of this area routine to disengage the negative electrode active material of lithium, material with carbon element for example, described material with carbon element be selected from non-graphitized charcoal, graphite or the charcoal that obtains by high-temperature oxydation by polyyne family macromolecule material or pyrolytic carbon, coke, organic polymer sinter, active carbon in one or more.Described organic polymer sinter can be by with products therefrom after sintering such as phenolic resins, epoxy resin and the charing.
The kind of described negative pole adhesive and content are conventionally known to one of skill in the art, for example one or more in fluorine resin and polyolefin compound such as polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), butadiene-styrene rubber (SBR), hydroxypropyl methylcellulose, sodium carboxymethylcellulose, hydroxyethylcellulose, the polyvinyl alcohol; In general, according to the difference of adhesive therefor kind, be benchmark with the weight of negative electrode active material, the content of negative pole adhesive is 0.01-8 weight %, is preferably 0.02-5 weight %.
Described negative material can also comprise that conductive agent to increase the conductivity of electrode, reduces the internal resistance of cell.Described conductive agent is not particularly limited, and can be the cathode conductive agent of this area routine, such as in carbon black, nickel powder, the copper powder one or more.Weight with negative electrode active material is benchmark, and the content of described conductive agent is 0-12 weight %, is preferably 2-10 weight %.
The negative pole conducting base can be for negative pole conducting base conventional in the lithium ion battery, as stamped metal, and metal forming, net metal, foamed metal uses Copper Foil as the negative pole conducting base in specific embodiments of the present invention.
The preparation method of described negative pole can adopt conventional preparation method.For example, with negative material and solvent, apply and/or be filled on the described conducting base, drying is rolled or is not rolled, and can obtain described negative pole.Wherein, described solvent can be selected from one or more in N-methyl pyrrolidone (NMP), dimethyl formamide (DMF), diethylformamide (DEF), dimethyl sulfoxide (DMSO) (DMSO), oxolane (THF) and water and the alcohols.The consumption of solvent can make described pastel have viscosity and flowability, can be coated on the described conducting base to get final product.In general, be benchmark with the weight of negative electrode active material, the content 30-90 weight % of described solvent is preferably 35-85 weight %.Wherein, drying, the method for calendering and condition are conventionally known to one of skill in the art.For example, the temperature of described drying is generally 100-150 ℃.
Described nonaqueous electrolytic solution is the mixed solution of electrolyte lithium salt and nonaqueous solvents, and it is not particularly limited, and can use the nonaqueous electrolytic solution of this area routine.Be selected from lithium hexafluoro phosphate (LiPF such as electrolyte lithium salt
6), in lithium perchlorate, LiBF4, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and the fluorocarbon based sulfonic acid lithium one or more.Organic solvent is selected chain acid esters and ring-type acid esters mixed solution for use, wherein the chain acid esters can be dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carbonic acid first propyl ester (MPC), dipropyl carbonate (DPC) and other are fluorine-containing, sulfur-bearing or contain at least a in the chain organosilane ester of unsaturated bond, the ring-type acid esters can be ethylene carbonate (EC), propene carbonate (PC), vinylene carbonate (VC), gamma-butyrolacton (γ-BL), sultone and other are fluorine-containing, sulfur-bearing or contain at least a in the ring-type organosilane ester of unsaturated bond.The injection rate of electrolyte is generally 1.5-4.9 gram/ampere-hour, the concentration of electrolyte be generally 0.1-2.0 rub/liter.
According to the preparation method of lithium ion battery provided by the invention, except described positive pole prepared according to method provided by the invention, other step was conventionally known to one of skill in the art.In general, described positive pole for preparing and negative pole winding are separated formation electrode group, electrode group and the electrolyte that obtains is sealed in the battery case, can obtain lithium ion battery provided by the invention by membrane layer.The method for winding of the membrane layer between positive pole and negative pole is conventionally known to one of skill in the art, does not repeat them here.
To the present invention be described in more detail by embodiment below.
Embodiment 1
This embodiment illustrates positive pole provided by the invention and contains this anodal lithium ion battery and their preparation method.
(1) Zheng Ji preparation
With 100 weight portion tap densities is 1.6 gram per centimeters
3Positive active material LiNi
0.33Co
0.33Mn
0.34O
2, 4 weight portion adhesive polyvinylidene fluoride (PVDF), 4 weight portion conductive agent acetylene blacks join in the 50 weight portion N-methyl pyrrolidones (NMP), in de-airing mixer, stir then and form uniform anode sizing agent.
This slurry is coated on wide 400 millimeters, the thick 20 microns aluminium foil equably, 120 ℃ of oven dry then, under the pressure of 1.6 MPas, on cutting machine, cut after the roll-in and obtain being of a size of 385 millimeters * 42 millimeters * 135 microns positive pole, wherein contain the anodal material of 4.42 grams, the dressing density of the positive plate that obtains is 3.4 gram per centimeters
3
(2) preparation of negative pole
100 weight portion negative electrode active material native graphites, 4 weight portion adhesive polytetrafluoroethylene (PTFE)s, 4 weight portion conductive agent carbon blacks are joined in the 45 weight portion methyl-sulfoxides (DMSO), in de-airing mixer, stir then and form cathode size stable, homogeneous.
This slurry is coated on wide 400 millimeters, the thick 10 microns Copper Foil equably, after 120 ℃ of oven dry, rolling, on cutting machine, cuts and obtain being of a size of 43 millimeters * 355 millimeters * 135 microns negative pole, wherein contain 2.7 gram negative pole material.
(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 polyethylene (PE), (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
This embodiment illustrates positive pole provided by the invention and contains this anodal lithium ion battery and their preparation method.
(1) Zheng Ji preparation
With 100 weight portion tap densities is 1.8 gram per centimeters
3Positive active material LiNi
0.33Co
0.33Mn
0.34O
2, 4 weight portion adhesive polyvinylidene fluoride (PVDF), 4 weight portion conductive agent acetylene blacks join in the 50 weight portion N-methyl pyrrolidones (NMP), in de-airing mixer, stir then and form uniform anode sizing agent.
This slurry is coated on wide 400 millimeters, the thick 20 microns aluminium foil equably, 120 ℃ of oven dry then, under the pressure of 1.8 MPas, on cutting machine, cut after the roll-in and obtain being of a size of 385 millimeters * 42 millimeters * 135 microns positive pole, wherein contain the anodal material of 4.39 grams, the dressing density of the positive plate that obtains is 3.5 gram per centimeters
3
(2) preparation of negative pole
100 weight portion negative electrode active material native graphites, 4 weight portion adhesive polytetrafluoroethylene (PTFE)s, 4 weight portion conductive agent carbon blacks are joined in the 45 weight portion methyl-sulfoxides (DMSO), in de-airing mixer, stir then and form cathode size stable, homogeneous.
This slurry is coated on wide 400 millimeters, the thick 10 microns Copper Foil equably, after 120 ℃ of oven dry, rolling, on cutting machine, cuts and obtain being of a size of 43 millimeters * 355 millimeters * 135 microns negative pole, wherein contain 2.7 gram negative pole material.
(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 polyethylene (PE), (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 A2 after the sealing.
Embodiment 3
This embodiment illustrates positive pole provided by the invention and contains this anodal lithium ion battery and their preparation method.
(1) Zheng Ji preparation
With 100 weight portion tap densities is 2.0 gram per centimeters
3Positive active material LiNi
0.33Co
0.33Mn
0.34O
2, 4 weight portion adhesive polyvinylidene fluoride (PVDF), 4 weight portion conductive agent acetylene blacks join in the 50 weight portion N-methyl pyrrolidones (NMP), in de-airing mixer, stir then and form uniform anode sizing agent.
This slurry is coated on wide 400 millimeters, the thick 20 microns aluminium foil equably, 120 ℃ of oven dry then, under the pressure of 2.0 MPas, on cutting machine, cut after the roll-in and obtain being of a size of 385 millimeters * 42 millimeters * 135 microns positive pole, wherein contain the anodal material of 4.38 grams, the dressing density of the positive plate that obtains is 3.6 gram per centimeters
3
(2) preparation of negative pole
100 weight portion negative electrode active material native graphites, 4 weight portion adhesive polytetrafluoroethylene (PTFE)s, 4 weight portion conductive agent carbon blacks are joined in the 45 weight portion methyl-sulfoxides (DMSO), in de-airing mixer, stir then and form cathode size stable, homogeneous.
This slurry is coated on wide 400 millimeters, the thick 10 microns Copper Foil equably, after 120 ℃ of oven dry, rolling, on cutting machine, cuts and obtain being of a size of 43 millimeters * 355 millimeters * 135 microns negative pole, wherein contain 2.7 gram negative pole material.
(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 polyethylene (PE), (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 A3 after the sealing.
Embodiment 4
This embodiment illustrates positive pole provided by the invention and contains this anodal lithium ion battery and their preparation method.
(1) Zheng Ji preparation
With 100 weight portion tap densities is 2.1 gram per centimeters
3Positive active material LiNi
0.33Co
0.33Mn
0.34O
2, 4 weight portion adhesive polyvinylidene fluoride (PVDF), 4 weight portion conductive agent acetylene blacks join in the 50 weight portion N-methyl pyrrolidones (NMP), in de-airing mixer, stir then and form uniform anode sizing agent.
This slurry is coated on wide 400 millimeters, the thick 20 microns aluminium foil equably, 120 ℃ of oven dry then, under the pressure of 2.2 MPas, on cutting machine, cut after the roll-in and obtain being of a size of 385 millimeters * 42 millimeters * 135 microns positive pole, wherein contain the anodal material of 4.41 grams, the dressing density of the positive plate that obtains is 3.7 gram per centimeters
3
(2) preparation of negative pole
100 weight portion negative electrode active material native graphites, 4 weight portion adhesive polytetrafluoroethylene (PTFE)s, 4 weight portion conductive agent carbon blacks are joined in the 45 weight portion methyl-sulfoxides (DMSO), in de-airing mixer, stir then and form cathode size stable, homogeneous.
This slurry is coated on wide 400 millimeters, the thick 10 microns Copper Foil equably, after 120 ℃ of oven dry, rolling, on cutting machine, cuts and obtain being of a size of 43 millimeters * 355 millimeters * 135 microns negative pole, wherein contain 2.7 gram negative pole material.
(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 polyethylene (PE), (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 A4 after the sealing.
Embodiment 5
This embodiment illustrates positive pole provided by the invention and contains this anodal lithium ion battery and their preparation method.
(1) Zheng Ji preparation
With 100 weight portion tap densities is 1.4 gram per centimeters
3Positive active material LiNi
0.33Co
0.33Mn
0.34O
2, 4 weight portion adhesive polyvinylidene fluoride (PVDF), 4 weight portion conductive agent acetylene blacks join in the 50 weight portion N-methyl pyrrolidones (NMP), in de-airing mixer, stir then and form uniform anode sizing agent.
This slurry is coated on wide 400 millimeters, the thick 20 microns aluminium foil equably, 120 ℃ of oven dry then, under the pressure of 2.5 MPas, on cutting machine, cut after the roll-in and obtain being of a size of 385 millimeters * 42 millimeters * 135 microns positive pole, wherein contain the anodal material of 4.43 grams, the dressing density of the positive plate that obtains is 3.8 gram per centimeters
3
(2) preparation of negative pole
100 weight portion negative electrode active material native graphites, 4 weight portion adhesive polytetrafluoroethylene (PTFE)s, 4 weight portion conductive agent carbon blacks are joined in the 45 weight portion methyl-sulfoxides (DMSO), in de-airing mixer, stir then and form cathode size stable, homogeneous.
This slurry is coated on wide 400 millimeters, the thick 10 microns Copper Foil equably, after 120 ℃ of oven dry, rolling, on cutting machine, cuts and obtain being of a size of 43 millimeters * 355 millimeters * 135 microns negative pole, wherein contain 2.7 gram negative pole material.
(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 polyethylene (PE), (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 A5 after the sealing.
Comparative Examples 1-2
This Comparative Examples explanation reference positive pole and lithium ion battery and their preparation method.
It is anodal and comprise this anodal lithium ion battery AC1-AC2 to prepare reference according to the content of the method identical with embodiment 1 and each material, and the dressing density of different is described positive plate is respectively 3.3 gram per centimeters
3With 3.9 gram per centimeters
3
Performance test
Battery capacity method of testing below adopting is measured the charge/discharge capacity of the lithium ion battery AC1-AC2 that lithium ion battery A1-A5 that embodiment 1-5 obtains and Comparative Examples 1-2 obtain respectively.The result is as shown in table 1.
The battery capacity method of testing: charge with constant voltage charging method, the restriction electric current is 0.1C (65mA), and final voltage is 4.4 volts; Discharge in the constant-current discharge mode, discharging current is 1C (650mA), and the cut-ff voltage of discharge is 3.0 volts.
The space availability ratio of battery refers to the size of battery capacity in the unit volume, promptly equals battery capacity/battery volume.The length x width x thickness of battery volume=battery, the battery length that obtains according to method of the present invention is 48 millimeters, width is 30 millimeters, so the space availability ratio=battery capacity of battery/battery length (48 millimeters) * cell widths (30 millimeters) * cell thickness (millimeter).The result is as shown in table 1.
Table 1
| The embodiment numbering | Dressing density (gram per centimeter 3) | Cell thickness (millimeter) | Charging capacity (mAh) | Discharge capacity (mAh) | Space availability ratio (mAh/mm 3)? |
| Embodiment 1 | 3.4 | 5.23 | 764 | 674 | 0.0895 |
| Embodiment 2 | 3.5 | 5.21 | 763 | 671 | 0.0894 |
| Embodiment 3 | 3.6 | 5.16 | 761 | 665 | 0.0895 |
| Embodiment 4 | 3.7 | 5.15 | 756 | 657 | 0.0886 |
| Embodiment 5 | 3.8 | 5.14 | 748 | 652 | 0.0881 |
| Comparative Examples 1 | 3.3 | 5.34 | 767 | 675 | 0.0877 |
| Comparative Examples 2 | 3.9 | — | — | — | — |
From the result of table 1 as can be seen, the cell thickness that Comparative Examples 1 obtains is thicker, therefore anodal material is more, thereby battery capacity is higher, but because dressing density is low, cell thickness is thick to make that the space availability ratio of battery is low, though and the dressing density of Comparative Examples 2 is high,, make pole piece become fragile because the big anodal material of dressing density is few, can't reel, thereby can't be prepared into battery.Compare with Comparative Examples 1-2, lithium ion battery provided by the invention has higher charge/discharge capacity and higher space availability ratio simultaneously, and battery performance is good.
Claims (12)
1, a kind of positive pole of lithium ion battery, this positive pole comprise conducting base and coating and/or be filled in positive electrode on the conducting base, and described positive electrode comprises positive active material, conductive agent and adhesive, and described positive active material is LiNi
xCo
yMn
1-x-yO
2, in the formula, 0.1≤x≤0.5,0.1≤y≤0.5 is characterized in that, the dressing density of described positive electrode is the 3.4-3.8 gram per centimeter
3
2, positive pole according to claim 1, wherein, the dressing density of described positive electrode is the 3.5-3.7 gram per centimeter
3
3, positive pole according to claim 1, wherein, the tap density of described positive active material is the 1.5-2.5 gram per centimeter
3
4, positive pole according to claim 3, wherein, the tap density of described positive active material is the 1.6-2.4 gram per centimeter
3
5, the preparation method of the described lithium ion cell positive of claim 1, this method comprises that the slurry that will contain positive electrode and solvent applies and/or is filled on the conducting base, dry, calendering, described positive electrode comprises positive active material, conductive agent and adhesive, and described positive active material is LiNi
xCo
yMn
1-x-yO
2, in the formula, 0.1≤x≤0.5,0.1≤y≤0.5 is characterized in that, it is the 3.4-3.8 gram per centimeter that the pressure of described calendering makes the dressing density of positive electrode
3
6, preparation method according to claim 5, wherein, it is the 3.5-3.7 gram per centimeter that the pressure of described calendering makes the dressing density of positive electrode
3
7, method according to claim 5, wherein, the tap density of described positive active material is the 1.5-2.5 gram per centimeter
3
8, method according to claim 7, wherein, the tap density of described positive active material is the 1.6-2.4 gram per centimeter
3
9, method according to claim 5, wherein, the pressure of described calendering is the 1.6-2.4 MPa.
10, a kind of lithium ion battery, this battery comprises electrode group and nonaqueous electrolytic solution, and described electrode group and nonaqueous electrolytic solution are sealed in the battery container, and described electrode group comprises positive pole, negative pole and barrier film, it is characterized in that any described positive pole among the described just very claim 1-4.
11, battery according to claim 10, wherein, the charging voltage of described battery is more than or equal to 4.3 volts.
12, the preparation method of the described battery of claim 10, this method comprises positive pole and the negative pole for preparing this battery, and positive pole, negative pole and barrier film are prepared into the electrode group, the electrode group and the electrolyte that obtain are sealed in the battery case, it is characterized in that any described positive pole among the described just very claim 1-4.
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