CN100511821C - A lithium ion battery and preparing method thereof - Google Patents
A lithium ion battery and preparing method thereof Download PDFInfo
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- CN100511821C CN100511821C CNB2005101148670A CN200510114867A CN100511821C CN 100511821 C CN100511821 C CN 100511821C CN B2005101148670 A CNB2005101148670 A CN B2005101148670A CN 200510114867 A CN200510114867 A CN 200510114867A CN 100511821 C CN100511821 C CN 100511821C
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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 lithium battery, which comprises electrode group and non-water electrolyte that sealed in battery frame, wherein the electrode group comprises anode, cathode, and baffle film; the anode comprises anode conductive substrate and the anode material coated and/or filled on conductive substrate; said anode material comprises active material and adhesive; the active material is LiNixCoyMn1-x-yO2 while 0.1<=x<=0.5, 0.1<=y<=0.5; the cathode comprises cathode conductive substrate and the cathode material coated and/or filled on conductive substrate; said cathode material comprises cathode active component and cathode adhesive, while the mass ration between anode and cathode active components is 0.5-2.2. The inventive lithium battery has better circulate property and high safety.
Description
Technical field
The invention relates to a kind of battery and preparation method thereof, specifically, the invention relates to a kind of lithium ion battery and preparation method thereof.
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 positive pole, negative pole and barrier film, described positive pole comprises anodal conducting base and coating and/or is filled in positive electrode on the anodal conducting base that described positive electrode comprises positive active material and anodal adhesive; Described negative pole comprises negative pole conducting base and coating and/or is filled in negative material on the negative pole conducting base that described negative material comprises negative electrode active material and negative pole adhesive.
Anode active material of lithium ion battery commonly used at present mainly contains lithium cobalt oxygen (LiCoO
2), lithium nickel oxygen (LiNiO
2) and nickel manganese oxygen (LiMn
2O
4).LiCoO
2Have good circulation (reversible discharging and recharging) and bigger discharge capacity (140mAh/g) greater than 500 times, but LiCoO
2The defective that can't remedy is arranged itself: the one, cobalt belongs to rare metal, and the reserves in the earth's crust are few, thereby cost an arm and a leg, and cobalt is poisonous simultaneously, and environment is had destruction; The 2nd, LiCoO
2Destroy at overcharge (charging voltage is higher than 4.2V) easy recurring structure, thermal stability is relatively poor, so charging voltage low (higher limit of charging voltage is 4.2V).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.LiMn
2O
4Synthetic simple, but specific capacity little (120mAh/g), and since the manganese ion of high price under higher temperature easily and electrolyte react so LiMn
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 disclose a class novel the lithium ion battery multi-element composite positive pole material, 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.The raising of charging voltage can improve anodal specific capacity, but under higher charging voltage, is easy to produce Li dendrite at negative pole, and Li dendrite might puncture diaphragm paper, and internal short-circuit takes place, thereby reduces the security performance of lithium ion battery.And the cycle performance of the lithium ion battery of this class composite positive pole of existing use is relatively poor.
Summary of the invention
The objective of the invention is to overcome existing use LiNiCoMnO
2The lithium ion battery security energy and the relatively poor shortcoming of cycle performance of composite material provide a kind of lithium ion battery with good safety energy and cycle performance and preparation method thereof.
The inventor finds, existing use LiNiCoMnO
2The lithium ion battery security energy and the relatively poor main cause of cycle performance of composite positive pole are, the capacity ratio of negative electrode active material and positive active material too low (being generally less than 1.1), the remaining capacity of negative pole very little, in the battery use, produce Li dendrite at negative pole easily and cause safety problem; And along with the consumption gradually of negative pole, the capacity of battery also descends gradually, thereby influences cycle performance.
The invention provides a kind of lithium ion battery, this lithium ion battery comprises electrode group and nonaqueous electrolytic solution, and 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 anodal conducting base and coating and/or is filled in positive electrode on the anodal conducting base, and described positive electrode comprises positive active material and anodal adhesive, and described positive active material is LiNi
xCo
yMn
1-x-yO
2, 0.1≤x≤0.5,0.1≤y≤0.5; Described negative pole comprises negative pole conducting base and coating and/or is filled in negative material on the negative pole conducting base, described negative material comprises negative electrode active material and negative pole adhesive, wherein, the weight ratio of described positive active material and negative electrode active material is 0.5-2.2.
The present invention also provides a kind of preparation method of lithium ion battery, and this method comprises:
The anode sizing agent that will contain positive electrode applies and/or is filled on the anodal conducting base, and drying is rolled or do not rolled, and obtains positive pole, and described positive electrode comprises positive active material and anodal adhesive, and described positive active material is LiNi
xCo
yMn
1-x-yO
2, 0.1≤x≤0.5,0.1≤y≤0.5
The cathode size that will contain negative material applies and/or is filled on the negative pole conducting base, and drying is rolled or do not rolled, and obtains negative pole, and described negative material comprises negative electrode active material and adhesive;
And positive pole, negative pole and barrier film are prepared into the electrode group, electrode group and the electrolyte that obtains are sealed in the battery case,
Wherein, the weight ratio of described positive active material and negative electrode active material is 0.5-2.2.
In the lithium ion battery provided by the invention, be controlled at 0.5-2.2 by weight ratio with positive active material and negative electrode active material, the capacity ratio that can make negative electrode active material and positive active material is more than or equal to 1.10, avoid in the battery use, producing Li dendrite, thereby improved the security performance of battery in negative terminal surface; And in cyclic process,,, therefore can not influence the cycle performance of battery because the capacity of negative electrode active material residue is more though negative pole is consumed gradually.
Embodiment
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; 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, and described positive electrode comprises positive active material and anodal adhesive, and described positive active material is LiNi
xCo
yMn
1-x-yO
2, 0.1≤x≤0.5,0.1≤y≤0.5; Described negative pole comprises negative pole conducting base and coating and/or is filled in negative material on the negative pole conducting base, described negative material comprises negative electrode active material and negative pole adhesive, wherein, the weight ratio of described positive active material and negative electrode active material is smaller or equal to 2.2.
Wherein, when the weight ratio of positive active material and negative electrode active material greater than 2.2 the time, then the Capacity Ratio of negative electrode active material and positive active material is less than 1.10, the remaining capacity of negative pole is few, produce Li dendrite in negative terminal surface easily, puncture diaphragm paper and cause internal short-circuit of battery, the cell safety problem takes place, capacity of negative plates remained low simultaneously, battery along with the consumption gradually of negative pole, causes the capacity of battery also to descend gradually in the middle of circulation, cycle performance is affected, and therefore the weight ratio of described positive active material and negative electrode active material is smaller or equal to 2.2.But the weight ratio of working as positive active material and negative electrode active material is too little, as less than 0.5, particularly less than 1.5 o'clock, then the Capacity Ratio of negative electrode active material and positive active material is greater than 1.25, negative pole is excessive too many, occupies too many inside battery space, influences battery capacity, therefore the weight ratio of described positive active material and negative electrode active material is preferably 1.5-2.2, more preferably 1.6-2.0.When the weight ratio of utmost point active material and negative electrode active material was 1.6-2.0, lithium ion battery also kept higher battery capacity when having excellent cycle performance and security performance.
According to the positive pole of lithium ion battery provided by the invention, described positive active material is LiNi
xCo
yMn
1-x-yO
2, 0.1≤x≤0.5,0.1≤y≤0.5 wherein.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.Because the positive active material of lithium ion battery provided by the invention is LiNi
xCo
yMn
1-x-yO
2, therefore the charging voltage of lithium ion battery provided by the invention is more than or equal to 4.4 volts.Charging voltage more than or equal to 4.4 volts situation under, described LiNi
xCo
yMn
1-x-yO
2Specific capacity be 170-190mAh/g.
The kind of described anodal 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 anodal adhesive is 0.01-8 weight %, is preferably 0.02-5 weight %.
Described positive electrode can also comprise anodal conductive agent, and described anodal conductive agent is not particularly limited, and can be the anodal conductive agent of this area routine, such as in acetylene black, conductive carbon black and the electrically conductive graphite one or more.Weight with positive active material is benchmark, and the content of described anodal conductive agent is 0-15 weight %, is preferably 2-10 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, Punching steel strip.In the specific embodiment of the present invention, use aluminium foil as anodal conducting base.
Negative pole according to lithium ion battery provided by the invention, described negative electrode active material is not particularly limited, can use embedding of this area routine to disengage the negative electrode active material of lithium, such as in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal, the silicon alloy one or more, preferred natural graphite.Charging voltage more than or equal to 4.4 volts situation under, the specific capacity of described native graphite is 360-380mAh/g.
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), the butadiene-styrene rubber (SBR); In general, according to the difference of adhesive therefor kind, be benchmark with the weight of negative electrode active material, the content of negative pole adhesive is 0.01-8 weight %, is preferably 0.02-5 weight %.
Described negative material can also comprise cathode conductive agent, and described cathode 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 0-15 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 the specific embodiment of the present invention.
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.
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 consumption 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 ion battery provided by the invention comprises:
The anode sizing agent that will contain positive electrode applies and/or is filled on the anodal conducting base, and drying is rolled or do not rolled, and obtains positive pole, and described positive electrode comprises positive active material and anodal adhesive, and described positive active material is LiNi
xCo
yMn
1-x-yO
2, 0.1≤x≤0.5,0.1≤y≤0.5;
The cathode size that will contain negative material applies and/or is filled on the negative pole conducting base, and drying is rolled or do not rolled, and obtains negative pole, and described negative material comprises negative electrode active material and adhesive;
And positive pole, negative pole and barrier film are prepared into the electrode group, electrode group and the electrolyte that obtains are sealed in the battery case,
Wherein, the weight ratio of described positive active material and negative electrode active material is smaller or equal to 2.2.
Described positive pole can adopt conventional preparation method.For example, with described positive electrode and solvent, apply and/or be filled on the anodal conducting base, drying is rolled or is not rolled, and can obtain described positive pole.Under the preferable case, anodal conductive agent and solvent that positive active material, anodal adhesive and selectivity are contained evenly form anode sizing agent, and this slurry is applied and/or is filled on the anodal conducting base, and drying is rolled or do not rolled.Wherein, 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.In general the weight with positive active material is benchmark, and 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.
Described negative pole can adopt conventional preparation method.For example, with negative material and solvent, apply and/or be filled on the negative pole conducting base, drying is rolled or is not rolled, and can obtain described negative pole.Under the preferable case, cathode conductive agent and solvent that negative electrode active material, negative pole adhesive and selectivity are contained evenly form cathode size, and this slurry is applied and/or is filled on the negative pole conducting base, and drying is rolled or do not rolled.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 ℃.
Make after described positive pole and the negative pole, 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 lithium ion battery provided by the invention and preparation method thereof.
(1) Zheng Ji preparation
With 100 weight portion positive active material LiNi
0.33Co
0.33Mn
0.34O
2, 4 weight portion adhesive PVDF, 5 weight portion conductive agent acetylene blacks join in the 40 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, and 120 ℃ of oven dry, roll-ins are cut on cutting machine and obtain being of a size of 385 millimeters * 42 millimeters * 135 microns positive pole afterwards then, wherein contain 4.8 gram cathode mixtures.
(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 40 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 2.9 gram negative pole compounds.
Wherein, the weight ratio of positive active material and negative electrode active material is 1.65.
(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
This embodiment illustrates lithium ion battery provided by the invention and preparation method thereof.
(1) Zheng Ji preparation
With 100 weight portion positive active material LiNi
0.1Co
0.1Mn
0.8O
2, 1 weight portion adhesive PVDF, 4 weight portion conductive agent acetylene blacks join in the 70 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, and 120 ℃ of oven dry, roll-ins are cut on cutting machine and obtain being of a size of 385 millimeters * 42 millimeters * 135 microns positive pole afterwards then, wherein contain 4.8 gram cathode mixtures.
(2) preparation of negative pole
100 weight portion negative electrode active material native graphites, 2 weight portion adhesive polytetrafluoroethylene (PTFE)s, 6 weight portion conductive agent carbon blacks are joined in the 70 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 2.8 gram negative pole compounds.
Wherein, the weight ratio of positive active material and negative electrode active material is 1.72.
(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 A2 after the sealing.
Embodiment 3
This embodiment illustrates lithium ion battery provided by the invention and preparation method thereof.
(1) Zheng Ji preparation
With 100 weight portion positive active material LiNi
0.45Co
0.45Mn
0.1O
2, 3 weight portion adhesive PVDF, 8 weight portion conductive agent acetylene blacks join in the 70 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, and 120 ℃ of oven dry, roll-ins are cut on cutting machine and obtain being of a size of 385 millimeters * 42 millimeters * 135 microns positive pole afterwards then, wherein contain 4.8 gram cathode mixtures.
(2) preparation of negative pole
100 weight portion negative electrode active material native graphites, 2 weight portion adhesive polytetrafluoroethylene (PTFE)s, 6 weight portion conductive agent carbon blacks are joined in the 70 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 compounds.
Wherein, the weight ratio of positive active material and negative electrode active material is 1.78.
(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 A3 after the sealing.
Embodiment 4
This embodiment illustrates lithium ion battery provided by the invention and preparation method thereof.
(1) Zheng Ji preparation
With 100 weight portion positive active material LiNi
0.2Co
0.2Mn
0.6O
2, 3 weight portion adhesive PVDF, 3 weight portion conductive agent acetylene blacks join in the 70 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, and 120 ℃ of oven dry, roll-ins are cut on cutting machine and obtain being of a size of 385 millimeters * 42 millimeters * 135 microns positive pole afterwards then, wherein contain 4.8 gram cathode mixtures.
(2) preparation of negative pole
100 weight portion negative electrode active material native graphites, 2 weight portion adhesive polytetrafluoroethylene (PTFE)s, 6 weight portion conductive agent carbon blacks are joined in the 70 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 2.6 gram negative pole compounds.
Wherein, the weight ratio of positive active material and negative electrode active material is 1.85.
(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 A4 after the sealing.
Embodiment 5
This embodiment illustrates lithium ion battery provided by the invention and preparation method thereof.
(1) Zheng Ji preparation
With 100 weight portion positive active material LiNi
0.15Co
0.35Mn
0.5O
2, 3 weight portion adhesive PVDF, 6 weight portion conductive agent acetylene blacks join in the 70 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, and 120 ℃ of oven dry, roll-ins are cut on cutting machine and obtain being of a size of 385 millimeters * 42 millimeters * 135 microns positive pole afterwards then, wherein contain 4.8 gram cathode mixtures.
(2) preparation of negative pole
100 weight portion negative electrode active material native graphites, 2 weight portion adhesive polytetrafluoroethylene (PTFE)s, 6 weight portion conductive agent carbon blacks are joined in the 70 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 2.5 gram negative pole compounds.
Wherein, the weight ratio of positive active material and negative electrode active material is 1.92.
(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 A5 after the sealing.
Comparative Examples 1
This Comparative Examples explanation reference positive pole and lithium ion battery and their preparation method thereof.
Prepare lithium ion battery AC1 according to the method identical with embodiment 1, the weight ratio of different is positive active material and negative electrode active material is 2.5.
Comparative example 2
This Comparative Examples explanation reference positive pole and lithium ion battery and their preparation method thereof.
Prepare lithium ion battery AC2 according to the method identical with embodiment 1, the weight ratio of different is positive active material and negative electrode active material is 1.4.
Performance test
Testing Method of Safety, battery capacity method of testing and cycle performance method of testing below adopting measured security performance, charge/discharge capacity and the cycle performance of the lithium ion battery AC1-AC3 that lithium ion battery A1-A5 that embodiment 1-5 obtains and Comparative Examples 1-3 obtain respectively, and the result is as shown in table 1.
Security performance test: 1C, 5V overcharge test, adopt the 1C electric current, constant voltage 5V test, when electric current stops during less than 50mA, battery does not explode or is on fire in this process, be by, otherwise for not passing through.
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, and is recorded in the discharge voltage of the mid point of discharge curve.
Loop test: under 23 ℃ of conditions, with battery respectively with the 1C current charges to 4.2V, with constant-potential charge, cut-off current is 0.05C after voltage rises to 4.4V, shelves 10 minutes; Battery, was shelved 5 minutes to 3.0V with the 1C current discharge.Repeat above step 500 time, obtain the capacity of 100 circulation backs of battery 1C current discharge to 3.0V, by capacity sustainment rate before and after the following formula computation cycles:
Capacity sustainment rate=(the 100th cyclic discharge capacity/cyclic discharge capacity) first * 100%
The cycle performance of the high expression of capacity sustainment rate battery is good, and the cycle performance of the low expression of capacity sustainment rate battery is poor.
Table 1
| The embodiment numbering | The battery numbering | The weight ratio of positive active material and negative electrode active material | Charging capacity (mAh) | Discharge capacity (mAh) | Capability retention (%) after 100 circulations | Security performance |
| Embodiment 1 | A1 | 1.65 | 753 | 659 | 95.3 | o |
| Embodiment 2 | A2 | 1.72 | 761 | 668 | 95.1 | o |
| Embodiment 3 | A3 | 1.78 | 762 | 671 | 95.2 | o |
| Embodiment 4 | A4 | 1.85 | 774 | 678 | 94.5 | o |
| Embodiment 5 | A5 | 1.92 | 780 | 685 | 94.1 | o |
| Comparative example 1 | AC1 | 2.5 | 797 | 704 | 90.1 | o |
| Comparative example 2 | AC2 | 1.4 | 710 | 632 | 95.3 | X |
Annotate: " o " expression is passed through, and " X " expression is not passed through.
From the result of table 1 as can be seen, though charging capacity and the discharge capacity of the lithium ion battery AC1 that comparative example 1 obtains are higher, the cycle performance of this battery and poor safety performance; Though cycle performance and the security performance of the lithium ion battery AC2 that comparative example 2 obtains are better, the charging capacity of this battery and discharge capacity are too low.Compare with the lithium ion battery that Comparative Examples 1-2 obtains, when the weight ratio of positive active material and negative electrode active material is between 1.6-2.0, lithium ion battery provided by the invention has excellent cycle performance and security performance, keeps higher charging capacity and discharge capacity simultaneously.
Claims (8)
1, 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 anodal conducting base and coating and/or is filled in positive electrode on the anodal conducting base, and described positive electrode comprises positive active material and anodal adhesive, and described positive active material is LiNi
xCo
yMn
1-x-yO
2, 0.1≤x≤0.5,0.1≤y≤0.5; Described negative pole comprises negative pole conducting base and coating and/or is filled in negative material on the negative pole conducting base, described negative material comprises negative electrode active material and negative pole adhesive, it is characterized in that the weight ratio of described positive active material and negative electrode active material is 1.5-2.2.
2, lithium ion battery according to claim 1, wherein, the weight ratio of described positive active material and negative electrode active material is 1.6-2.0.
3, lithium ion battery according to claim 1, wherein, described negative electrode active material is selected from one or more in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal, the silicon alloy.
4, lithium ion battery according to claim 1, wherein, described positive electrode also comprises anodal conductive agent, described anodal conductive agent is selected from one or more in acetylene black, conductive carbon black and the electrically conductive graphite; Weight with positive active material is benchmark, and the content of described anodal conductive agent is 2-10 weight %.
5, lithium ion battery according to claim 1, wherein, described negative material also comprises cathode conductive agent, described cathode conductive agent is selected from one or more in carbon black, nickel powder, the copper powder; Weight with negative electrode active material is benchmark, and the content of described cathode conductive agent is 2-10 weight %.
6, a kind of preparation method of lithium ion battery, this method comprises:
The anode sizing agent that will contain positive electrode applies and/or is filled on the anodal conducting base, and drying is rolled or do not rolled, and obtains positive pole, and described positive electrode comprises positive active material and anodal adhesive, and described positive active material is LiNi
xCo
yMn
1-x-yO
2, 0.1≤x≤0.5,0.1≤y≤0.5;
The cathode size that will contain negative material applies and/or is filled on the negative pole conducting base, and drying is rolled or do not rolled, and obtains negative pole, and described negative material comprises negative electrode active material and adhesive;
And positive pole, negative pole and barrier film are prepared into the electrode group, electrode group and the electrolyte that obtains are sealed in the battery case,
It is characterized in that the weight ratio of described positive active material and negative electrode active material is 1.5-2.2.
7, method according to claim 6, wherein, the weight ratio of described positive active material and negative electrode active material is 1.6-2.0.
8, method according to claim 6, wherein, described negative electrode active material is selected from one or more in native graphite, Delanium, petroleum coke, organic cracking carbon, carbonaceous mesophase spherules, carbon fiber, ashbury metal, the silicon alloy.
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| CN101504978B (en) * | 2009-03-19 | 2011-11-09 | 厦门钨业股份有限公司 | Lithium ionic cell positive plate made from ternary material and production method thereof |
| CN102956357B (en) * | 2012-11-06 | 2015-04-08 | 中国科学院电工研究所 | Li-ion supercapacitor |
| CN103746151A (en) * | 2013-12-07 | 2014-04-23 | 新余英泰能科技有限公司 | Method capable of enabling electronic cigarette battery to pass needling detection |
| CN103779600B (en) * | 2013-12-19 | 2016-08-17 | 宁波维科电池股份有限公司 | A kind of lithium titanate battery and manufacture method |
| CN108539198B (en) * | 2017-03-03 | 2023-02-28 | 易案爱富科技有限公司 | Solvent for coating positive electrode active material for secondary battery, positive electrode active material slurry containing same, and secondary battery manufactured therefrom |
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Non-Patent Citations (2)
| Title |
|---|
| Synthesis and characterization of LiCoxMnyNi1-x-yO2 as acathode material for secondary lithium batteries. Yao Chen, et al.Journal of Power Sources,Vol.119-121 . 2003 |
| Synthesis and characterization of LiCoxMnyNi1-x-yO2 as acathode material for secondary lithium batteries. Yao Chen, et al.Journal of Power Sources,Vol.119-121. 2003 * |
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