CN103746143A - High energy density lithium ion power battery - Google Patents

High energy density lithium ion power battery Download PDF

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Publication number
CN103746143A
CN103746143A CN201310663928.3A CN201310663928A CN103746143A CN 103746143 A CN103746143 A CN 103746143A CN 201310663928 A CN201310663928 A CN 201310663928A CN 103746143 A CN103746143 A CN 103746143A
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energy density
lithium ion
high energy
salt
electrokinetic cell
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颜雪冬
马兴立
潘美姿
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NINGBO VEKEN BATTERY CO Ltd
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NINGBO VEKEN BATTERY CO Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • 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 the technical field of a lithium ion power battery, and particularly relates to a high energy density lithium ion power battery including a positive electrode, a diaphragm, a negative electrode and an electrolyte, the negative electrode includes a negative electrode current collector and a negative electrode active material, the negative electrode active material is a Si-SnC2O4 high capacity composite material, and a positive electrode active material is high nickel and high capacity of ternary material Li[n]Ni[x]A[y]B[z]O[2]. The battery energy density, the battery charging cut-off voltage and the battery room temperature high pressure cycling performance of the high energy density lithium ion power battery are improved substantially.

Description

High energy density lithium ion electrokinetic cell
Technical field
The present invention relates to lithium-ion-power cell technical field, be specifically related to a kind of high energy density lithium ion electrokinetic cell.
Background technology
Lithium-ion-power cell relatively other batteries to have voltage high, energy density is large, good cycle, self discharge is little, memory-less effect, the advantage such as operating temperature range is wide.The structure of general lithium-ion-power cell is: with laminar, by battery core alternate to positive plate, barrier film, negative plate and that form (or making battery core with coiling form), then connect outside terminal, put into duricrust (for example moulding shell, box hat, aluminum hull) or aluminum plastic film, inject electrolyte.Tradition lithium-ion-power cell, the anodal general materials such as nickle cobalt lithium manganate, LiFePO4, LiMn2O4, cobalt acid lithium that adopt, negative pole adopts traditional graphite type material, such as Delanium, native graphite, hard carbon or soft carbon etc.; Electrolyte solvent generally adopts ethylene carbonate, propene carbonate, methyl ethyl carbonate, the materials such as diethyl carbonate, discharging and recharging cut-ff voltage scope is 2.7-4.2V, exactly because the energy density of current lithium-ion-power cell is restricted, affect lithium-ion-power cell and discharged and recharged cut-ff voltage, limited the application of lithium-ion-power cell.
Summary of the invention
The object of the invention is in order to overcome current lithium-ion-power cell because energy density is not better promoted, thereby causing discharging and recharging cut-ff voltage can not break through in lower scope, greatly limited the problem of the application of lithium-ion-power cell, a kind of high energy density lithium ion electrokinetic cell is provided.Technical scheme of the present invention, by adopting the material of high power capacity as the both positive and negative polarity of battery, has improved the energy density of battery, thereby has improved charge cutoff voltage and the normal temperature high voltage cycle performance of battery.
In order to reach foregoing invention object, the present invention by the following technical solutions:
A kind of high energy density lithium ion electrokinetic cell, comprises positive pole, barrier film, negative pole and electrolyte, and positive pole comprises plus plate current-collecting body and positive electrode active materials, and positive electrode active materials is nickelic high power capacity ternary material, and described nickelic high power capacity ternary material is Li nni xa yb zo 2, wherein: 1.0≤n≤1.1,0.7≤x≤0.8,0≤y≤0.15,0≤z≤0.15, and x+y+z=1.
One of business-like obstacle of electric automobile is that course continuation mileage is shorter.By positive pole and the negative pole of collocation high-energy-density, can improve to greatest extent the energy density of made battery, thus the course continuation mileage of prolongation electric automobile by a relatively large margin.
The high capacity density lithium-ion-power cell of existing market, generally adopts Li nni 0.5co 0.2mn 0.3o 2, wherein: 1.0≤n≤1.1,0.7≤x≤0.8 of the present invention, by adopting the positive electrode of nickelic high power capacity, may further improve the energy density of battery.
The general molecular formula of nickelic ternary material is Li nni xa yb zo 2.The Li that business-like electrokinetic cell is used nni xa yb zo 2material, general x≤0.5.In order to improve discharge performance, mainly by two aspects, realize at present, the first, reduce grain diameter, and particle diameter is generally 200-400nm, grain diameter is less, the conductivity of material is better, and high rate performance is better, but along with the reduction of grain diameter, the security performance of battery reduces, and the phenomenons such as acupuncture is on fire easily occur; Second, improve addition, but along with the increase of nickelic ternary material content in material, although the energy density of raising material that can be by a relatively large margin, but in cyclic process, cause micron order material structure unstable, deoxidation phenomenon easily occurs, affect cycle performance of battery, even if can carry out anodal film forming improvement by electrolysis additive, but cannot fundamentally solve the poor problem of the large current cycle of nickelic micron order material.And the present invention reaches by improving x the energy density that increases material, conductivity and high rate performance have been improved, and particle diameter is between 1-2 μ m, and the adverse effect of having avoided granule particle diameter to bring, has also avoided the excessive adverse effect to battery of bringing of nickelic ternary material addition simultaneously.
The nickelic ternary material using in this programme, primary particle particle diameter is 1-2 μ m, and conventional ternary material is 200-400 nanometer.By controlling the content of Li metal in material, reduce the pH value of material, improve drawing abillity; By preparing bulky grain material, optimize microcosmic layer structure, increase the stability of material structure, improve the large current cycle performance of material.
As preferably, described A and B are respectively the one in metallic element Co, Mn and Al.
As preferably, the preparation method of described nickelic high power capacity ternary material is:
(1) preparing hydrogen oxide precursor: together with two kinds in three kinds of soluble nickel salt and cobalt salt, manganese salt or aluminium salt, carry out precipitation reaction with the sodium hydroxide solution that is mixed with ammoniacal liquor, formation structural formula is Ni xa yb z(OH) 2granular precursor, wherein: x+y+z=1,0.7≤x≤0.8,0≤y≤0.15,0≤z≤0.15, A and B are respectively the one in metallic element Co, Mn and Al; Then through washing, dry, obtain hydroxide presoma; In this reaction, the concentration of ammoniacal liquor is controlled at 0.4-0.6mol/L, and NaOH is controlled at 4-6mol/L, and terminal pH value is controlled at 7.6-8.0, and the primary particle particle diameter of precursor is controlled at 1-2 μ m;
(2) by the hydroxide presoma obtaining and lithium salts take mol ratio as Li/ (Ni+A+B)=1.1-1.3, mix, make it to mix;
(3) high-temperature process: will carry out high-temperature process under the mixture nitrogen protection of upper step gained; The sintering temperature of high-temperature process is 1000-1200 ℃, and adopts ladder mode of heating, and initial stage sintering temperature is controlled at 900-1100 ℃, and later stage sintering temperature is controlled at 1100-1200 ℃; Then cooling, pulverize, sieve and obtain nickelic ternary anode material for lithium-ion batteries.
As preferably, negative pole comprises negative current collector and negative active core-shell material, and negative active core-shell material is C-Sn-Si high power capacity composite material.
Lithium-ion-power cell is used graphite material as negative pole at present.Conventionally the theoretical capacity of graphite material is 372mAh/g, commercially produced product peak capacity all≤365mAh/g, this has just limited to a certain extent and has adopted the energy density of the battery of graphite cathode made, and then has limited the performance of battery.And C-Sn-Si high power capacity composite material has higher capacity, its theoretical capacity is in 2000 about mAh/g, at present actually can reach 400-800 mAh/g.Therefore adopt this material can effectively improve the energy density of battery, and then improve the performance of battery.
As preferably, described C-Sn-Si high power capacity composite material is Si-SnC 2o 4, energy density>=500mAh/g.
The energy density of C-Sn-Si is higher, but cycle performance is but poor than graphite material.Si-SnC prepared by the present invention 2o 4material, can effectively improve the cycle performance of C-Sn-Si material.
As preferably, described Si-SnC 2o 4by following steps, be prepared from:
(1) get the silica flour that a certain amount of particle diameter is 0.1-5 μ m, by Si-SnC 2o 4middle Si and SnC 2o 4mass ratio be the solubility tin salt that 1-10:1 calculated and got aequum, by soluble in water to silica flour and solubility tin salt, stir, obtain suspension-turbid liquid, by soluble in water Soluble oxalate salt, obtain Soluble oxalate salting liquid;
(2) by the mol ratio of solubility tin salt and Soluble oxalate salt, be 1:1-1.3, Soluble oxalate salting liquid is poured in suspension-turbid liquid and constantly stirred 1-3h, obtain reactant liquor, by acid solution, regulating the pH of whole reaction system is 0.5-3.
(3) reactant liquor is carried out to Separation of Solid and Liquid, the solid obtaining, through washing and after temperature is to dry at 80-100 ℃, obtains Si-SnC 2o 4.
As preferably, described solubility tin salt is stannous chloride or stannous sulfate, and described Soluble oxalate salt is potassium oxalate, sodium oxalate or ammonium oxalate.
As preferably, described electrolyte comprises 3-5 kind functional additive, and the mass percent that every kind of functional additive accounts for electrolyte is W%, 1.0≤W≤5.0; The mass percent that the total amount of all functions additive accounts for electrolyte is N%, 5.0≤N≤15.
The addition of functional additive is very few, does not have circulation, the high-temperature behavior of due raising battery; Addition is too much, and the cost of electrolyte can increase, and can reduce the conductivity of electrolyte simultaneously, affects the high rate during charging-discharging of battery.
As preferably, described functional additive is selected from any 3-5 kind in vinylene carbonate (VC), propylene sulfite, fluorinated ethylene carbonate (FEC), vinylethylene carbonate (VEC) and catechol carbonic ester (CC).
Compared with prior art, beneficial effect is in the present invention: 1) the nickelic high power capacity ternary material of anodal use has improved 16% left and right by energy content of battery density; 2) negative pole is used C-Sn-Si high power capacity composite material, makes energy content of battery density improve 14% left and right; 3) by coordinating the compound high-voltage functions electrolyte of functional additive, make battery charge cutoff voltage bring up to 4.3V, and the normal temperature high voltage cycle performance of battery has improved 25% left and right.
Embodiment
Below by specific embodiment, technical scheme of the present invention is further described to explanation.
If without specified otherwise, the raw material adopting in embodiments of the invention is the conventional raw material in this area, and the method adopting in embodiment is the conventional method of this area.
24 preparation:
(1) get the silica flour that a certain amount of particle diameter is 0.1-5 μ m, by Si-SnC 2o 4middle Si and SnC 2o 4mass ratio be the solubility tin salt that 1-10:1 calculated and got aequum, by soluble in water to silica flour and solubility tin salt (stannous chloride or stannous sulfate), stir, obtain suspension-turbid liquid, by soluble in water Soluble oxalate salt (potassium oxalate, sodium oxalate or ammonium oxalate), obtain Soluble oxalate salting liquid;
(2) by the mol ratio of solubility tin salt and Soluble oxalate salt, be 1:1-1.3, Soluble oxalate salting liquid being poured in suspension-turbid liquid and regulate the pH of whole reaction system is 0.5-3, constantly stirs 1-3h, obtains reactant liquor;
(3) reactant liquor is carried out to Separation of Solid and Liquid, the solid obtaining, through washing and after temperature is to dry at 80-100 ℃, obtains Si-SnC 2o 4.
the preparation of nickelic high power capacity ternary material:
(1) preparing hydrogen oxide precursor: together with two kinds in three kinds of soluble nickel salt and cobalt salt, manganese salt or aluminium salt, carry out precipitation reaction with the sodium hydroxide solution that is mixed with ammoniacal liquor, formation structural formula is Ni xa yb z(OH) 2granular precursor, wherein: x+y+z=1,0.7≤x≤0.8,0≤y≤0.15,0≤z≤0.15, A and B are respectively the one in metallic element Co, Mn and Al; Then through washing, dry, obtain hydroxide presoma; In this reaction, the concentration of ammoniacal liquor is controlled at 0.4-0.6mol/L, and NaOH is controlled at 4-6mol/L, and terminal pH value is controlled at 7.6-8.0, and the primary particle particle diameter of precursor is controlled at 1-2 μ m;
(2) by the hydroxide presoma obtaining and lithium salts take mol ratio as Li/ (Ni+A+B)=1.1-1.3, mix, make it to mix;
(3) high-temperature process: will carry out high-temperature process under the mixture nitrogen protection of upper step gained; The sintering temperature of high-temperature process is 1000-1200 ℃, and adopts ladder mode of heating, and initial stage sintering temperature is controlled at 900-1100 ℃, and later stage sintering temperature is controlled at 1100-1200 ℃; Then cooling, pulverize, sieve and obtain nickelic ternary anode material for lithium-ion batteries.
The Si-SnC preparing by said method 2o 4for following embodiment.
Comparative example 1
Prepare anode pole piece: according to the nickle cobalt lithium manganate (Ni of 92 weight portions 5co 2mn 3o 2), the conductive black SP of 2 weight portions, the carbon nano-tube (CNT) of 2 weight portions, the Kynoar (PVDF) of 4 weight portions, the proportioning of the N-N-dimethyl pyrrolidone of 80 weight portions stirs and forms slurries, be coated in uniformly on anodal base flow body rolling aluminum foil, after being dried, with roller, roll, make anode pole piece.
Prepare cathode pole piece: the Delanium that mixes 95 weight portions, the conductive black SP of 1 weight portion, the sodium carboxymethylcellulose (CMC) of 1.5 weight portions and the butadiene-styrene rubber (SBR) of 2.5 weight portions, and the deionized water and stirring of adding 140 weight portions forms slurries, be coated in uniformly on negative pole base flow body electrolytic copper foil, after dry, with roller, roll, make cathode pole piece.
Prepare barrier film: barrier film employing thickness is the microporous compound film (PP-PE-PP) of 25 microns.
Prepare electrolyte: electrolyte adopts the lithium hexafluoro phosphate of 1.3mol/L to be dissolved in the ORGANIC SOLVENT MIXTURES of dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate ester, and wherein the volume ratio of dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate ester is (40:40:10:10).
Prepare shell: shell adopts aluminum plastic film, aluminum plastic film employing thickness is 152 microns and has nylon layer, tack coat, PP layer, tack coat, aluminium foil, tack coat, PP shape sandwich layer by layer.
Prepare external terminal: positive terminal adopts 0.2 millimeters thick aluminium material lug, negative terminal adopts 0.2 millimeter of copper nickel plating lug.
Prepare battery: with laminar, anode pole piece, barrier film, the alternate lamination of cathode pole piece are formed to battery core, unidirectional soldering polar ear; Then carry out aluminum plastic film heat-sealing, inject electrolyte, heat-sealing sealing; Shelve successively-preliminary filling-find time-change into-partial volume, make 30Ah lithium-ion-power cell.
Embodiment 1
Prepare anode pole piece: the nickelic high power capacity ternary material (Li that mixes 92 weight portions 1.04ni 0.8co 0.15al 0.05o 2), the conductive black SP of 2 weight portions, the carbon nano-tube (CNT) of 2 weight portions, and the Kynoar of 4 weight portions (PVDF), and the N-N-dimethyl pyrrolidone that adds 80 weight portions stirs formation slurries, be coated in uniformly on anodal base flow body rolling aluminum foil, after being dried, with roller, roll, make anode pole piece.
Prepare cathode pole piece: the C-Sn-Si high power capacity composite material (Si-SnC that mixes 90 weight portions 2o 4), the Kynoar (PVDF) of the conductive black SP of 2 weight portions and 8 weight portions, and add 140 weight portions N-N-dimethyl pyrrolidone stir form slurries, be coated in uniformly on negative pole base flow body electrolytic copper foil, after dry, with roller, roll, make cathode pole piece.
Prepare barrier film: barrier film employing thickness is the microporous compound film (PP-PE-PP) of 25 microns.
Prepare electrolyte: electrolyte adopts the lithium hexafluoro phosphate of 1.3mol/L to be dissolved in the ORGANIC SOLVENT MIXTURES of dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate ester, and wherein the volume ratio of dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate ester is (40:40:10:10); Add functional additive fluorinated ethylene carbonate (FEC), vinylethylene carbonate (VEC), catechol carbonic ester (CC), the mass percent that each functional additive accounts for electrolyte is respectively: 5%, 3%, 1.5%.
Prepare shell: shell adopts aluminum plastic film, aluminum plastic film employing thickness is 152 microns and has nylon layer, tack coat, PP layer, tack coat, aluminium foil, tack coat, PP shape sandwich layer by layer.
Prepare external terminal: positive terminal adopts 0.2 millimeters thick aluminium material lug, negative terminal adopts 0.2 millimeter of copper nickel plating lug.
Prepare battery: with laminar, anode pole piece, barrier film, the alternate lamination of cathode pole piece are formed to battery core, unidirectional soldering polar ear; Then carry out aluminum plastic film heat-sealing, inject electrolyte, heat-sealing sealing; Shelve successively-preliminary filling-find time-change into-partial volume, make 30Ah lithium-ion-power cell.
Embodiment 2
Prepare anode pole piece: the nickelic high power capacity ternary material (Li that mixes 92 weight portions 1.04ni 0.8co 0.15al 0.05o 2), the conductive black SP of 2 weight portions, the carbon nano-tube (CNT) of 2 weight portions, and the Kynoar of 4 weight portions (PVDF), and the N-N-dimethyl pyrrolidone that adds 80 weight portions stirs formation slurries, be coated in uniformly on anodal base flow body rolling aluminum foil, after being dried, with roller, roll, make anode pole piece.
Prepare cathode pole piece: the C-Sn-Si high power capacity composite material (Si-SnC that mixes 92 weight portions 2o 4), the conductive black SP of 2 weight portions and the polyacrylic acid of 6 weight portions, and the deionized water and stirring of adding 130 weight portions forms slurries, is coated in uniformly on negative pole base flow body electrolytic copper foil, roll with roller after dry, makes cathode pole piece.
Prepare barrier film: barrier film employing thickness is the microporous compound film (PP-PE-PP) of 25 microns.
Prepare electrolyte: electrolyte adopts the lithium hexafluoro phosphate of 1.3mol/L to be dissolved in the ORGANIC SOLVENT MIXTURES of dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate ester, and wherein the volume ratio of dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate ester is (40:40:10:10); Add functional additive: fluorinated ethylene carbonate (FEC), vinylethylene carbonate (VEC), vinylene carbonate (VC), the mass percent that each functional additive accounts for electrolyte is respectively: 5%, 3%, 3.5%.
Prepare shell: shell adopts aluminum plastic film, aluminum plastic film employing thickness is 152 microns and has nylon layer, tack coat, PP layer, tack coat, aluminium foil, tack coat, PP shape sandwich layer by layer.
Prepare external terminal: positive terminal adopts 0.2 millimeters thick aluminium material lug, negative terminal adopts 0.2 millimeter of copper nickel plating lug.
Prepare battery: with laminar, anode pole piece, barrier film, the alternate lamination of cathode pole piece are formed to battery core, unidirectional soldering polar ear; Then carry out aluminum plastic film heat-sealing, inject electrolyte, heat-sealing sealing; Shelve successively-preliminary filling-find time-change into-partial volume, make 30Ah lithium-ion-power cell.
Embodiment 3
Prepare anode pole piece: the nickelic high power capacity ternary material (Li that mixes 92 weight portions 1.03ni 0.8co 0.1mn 0.1o 2), the conductive black SP of 2 weight portions, the carbon nano-tube (CNT) of 2 weight portions, and the Kynoar of 4 weight portions (PVDF), and the N-N-dimethyl pyrrolidone that adds 80 weight portions stirs formation slurries, be coated in uniformly on anodal base flow body rolling aluminum foil, after being dried, with roller, roll, make anode pole piece.
Prepare cathode pole piece: the C-Sn-Si high power capacity composite material (Si-SnC that mixes 92 weight portions 2o 4), the conductive black SP of 2 weight portions and the polyacrylic acid of 6 weight portions, and the deionized water and stirring of adding 130 weight portions forms slurries, is coated in uniformly on negative pole base flow body electrolytic copper foil, roll with roller after dry, makes cathode pole piece.
Prepare barrier film: barrier film employing thickness is the microporous compound film (PP-PE-PP) of 25 microns.
Prepare electrolyte: electrolyte adopts the lithium hexafluoro phosphate of 1.3mol/L to be dissolved in the ORGANIC SOLVENT MIXTURES of dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate ester, and wherein the volume ratio of dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, propylene carbonate ester is (40:40:10:10); Add functional additive: vinylene carbonate (VC), propylene sulfite, fluorinated ethylene carbonate (FEC), vinylethylene carbonate (VEC) and catechol carbonic ester (CC), the mass percent that each functional additive accounts for electrolyte is respectively: 3%, 1%, 3.5%, 5%, 2%.
Prepare shell: shell adopts aluminum plastic film, aluminum plastic film employing thickness is 152 microns and has nylon layer, tack coat, PP layer, tack coat, aluminium foil, tack coat, PP shape sandwich layer by layer.
Prepare external terminal: positive terminal adopts 0.2 millimeters thick aluminium material lug, negative terminal adopts 0.2 millimeter of copper nickel plating lug.
Prepare battery: with laminar, anode pole piece, barrier film, the alternate lamination of cathode pole piece are formed to battery core, unidirectional soldering polar ear; Then carry out aluminum plastic film heat-sealing, inject electrolyte, heat-sealing sealing; Shelve successively-preliminary filling-find time-change into-partial volume, make 30Ah lithium-ion-power cell.
performance comparison
1, energy density test:
The battery that the various embodiments described above and comparative example 1 are made is respectively got 3 and is measured 25 ℃ of energy densities.Assay method is: at 25 ℃ by electric current with 15A constant current charge to 4.3V, then turn constant voltage charge, by electric current 3000mA; Shelve 10 minutes, with 15A constant current, be discharged to assigned voltage, measure the discharge capacity that obtains battery; Shelve after 10 minutes, repeat above-mentioned steps 3 times, calculate 3 times discharge capacity mean value.Service precision is the weight of the dissimilar battery of electronic balance weighing of 0.1g.Calculate according to the following formula 25 ℃ of energy content of battery density:
Energy content of battery density=electric discharge average size × 3.6V/ battery weight.
Energy content of battery density measurement the results are shown in Table 1.
As seen from the table, each embodiment energy content of battery density is 236-245Wh/Kg, and comparative example 1 energy content of battery density is 180 Wh/Kg.Embodiment test result is far superior to comparative example 1, and the battery that this explanation adopts this invention to make has increased substantially the energy density of battery.
, the test of 25 ℃-4.3V life performance:
The battery that above-mentioned comparative example 1 and each embodiment are made is respectively got 3, and measures the capacity surplus ratio after circulation 500 times.Assay method is: at 25 ℃ by electric current with 15A constant current charge to 4.3V, then turn constant voltage charge, by electric current 3000mA; Shelve 10 minutes, with 15A constant current, be discharged to assigned voltage, measure the initial discharge capacity that obtains battery; Shelve after 10 minutes, repeat above-mentioned steps 500 times, make continuous charge-discharge test, obtain the capacity surplus ratio after 500 circulations of battery, calculate according to the following formula the capacity surplus ratio of 500 rear batteries of circulation.
Discharge capacity/initial discharge capacity × 100% after time circulation of capacity surplus ratio=500.
Cycle life performance test result is in Table 1.As seen from the table, the capacity surplus ratio of embodiment after 500 circulations is at 83.3%-85.4%, and the capacity attenuation of comparative example 1 after 500 circulations is 80.2%.Embodiment test result is far superior to comparative example 1, the cycle of higher pressure life-span that the battery that this explanation adopts this invention to make has improved battery.
Table 1 battery performance contrast table
Test item Energy content of battery density (Wh/Kg) Capacity surplus ratio (%) after 25 ℃ of-500 circulations
Comparative example 1 180 80.2%
Embodiment 1 240 83.3%
Embodiment 2 245 84.7%
Embodiment 3 236 85.4%
Above-described embodiment, just for description and interpretation content of the present invention, can not form limitation of the scope of the invention.Although inventor has done in more detail and has enumerated the present invention, but, the content that those skilled in the art discloses according to summary of the invention part and embodiment, can make various modifications or/and to supplement or adopt similar mode to substitute be obvious to described specific embodiment.

Claims (9)

1. a high energy density lithium ion electrokinetic cell, comprise positive pole, barrier film, negative pole and electrolyte, it is characterized in that, positive pole comprises plus plate current-collecting body and positive electrode active materials, positive electrode active materials is nickelic high power capacity ternary material, and described nickelic high power capacity ternary material is Li nni xa yb zo 2, wherein: 1.0≤n≤1.1,0.7≤x≤0.8,0≤y≤0.15,0≤z≤0.15, and x+y+z=1.
2. high energy density lithium ion electrokinetic cell according to claim 1, is characterized in that, described A and B are respectively the one in metallic element Co, Mn and Al.
3. high energy density lithium ion electrokinetic cell according to claim 1, is characterized in that, the preparation method of described nickelic high power capacity ternary material is:
(1) preparing hydrogen oxide precursor: together with two kinds in three kinds of soluble nickel salt and cobalt salt, manganese salt or aluminium salt, carry out precipitation reaction with the sodium hydroxide solution that is mixed with ammoniacal liquor, formation structural formula is Ni xa yb z(OH) 2granular precursor, wherein: x+y+z=1,0.7≤x≤0.8,0≤y≤0.15,0≤z≤0.15, A and B are respectively the one in metallic element Co, Mn and Al; Then through washing, dry, obtain hydroxide presoma; In this reaction, the concentration of ammoniacal liquor is controlled at 0.4-0.6mol/L, and NaOH is controlled at 4-6mol/L, and terminal pH value is controlled at 7.6-8.0, and the primary particle particle diameter of precursor is controlled at 1-2 μ m;
(2) by the hydroxide presoma obtaining and lithium salts take mol ratio as Li/ (Ni+A+B)=1.1-1.3, mix, make it to mix;
(3) high-temperature process: will carry out high-temperature process under the mixture nitrogen protection of upper step gained; The sintering temperature of high-temperature process is 1000-1200 ℃, and adopts ladder mode of heating, and initial stage sintering temperature is controlled at 900-1100 ℃, and later stage sintering temperature is controlled at 1100-1200 ℃; Then cooling, pulverize, sieve and obtain nickelic ternary anode material for lithium-ion batteries.
4. high energy density lithium ion electrokinetic cell according to claim 1, is characterized in that, negative pole comprises negative current collector and negative active core-shell material, and negative active core-shell material is C-Sn-Si high power capacity composite material.
5. high energy density lithium ion electrokinetic cell according to claim 1, is characterized in that, described C-Sn-Si high power capacity composite material is Si-SnC 2o 4, energy density>=500mAh/g.
6. according to the high energy density lithium ion electrokinetic cell described in claim 4 or 5, it is characterized in that described Si-SnC 2o 4by following steps, be prepared from:
(1) get the silica flour that a certain amount of particle diameter is 0.1-5 μ m, by Si-SnC 2o 4middle Si and SnC 2o 4mass ratio be the solubility tin salt that 1-10:1 calculated and got aequum, by soluble in water to silica flour and solubility tin salt, stir, obtain suspension-turbid liquid, by soluble in water Soluble oxalate salt, obtain Soluble oxalate salting liquid;
(2) by the mol ratio of solubility tin salt and Soluble oxalate salt, be 1:1-1.3, Soluble oxalate salting liquid is poured in suspension-turbid liquid and constantly stirred 1-3h, obtain reactant liquor; By acid solution, regulating the pH of whole reaction system is 0.5-3;
(3) reactant liquor is carried out to Separation of Solid and Liquid, the solid obtaining, through washing and after temperature is to dry at 80-100 ℃, obtains Si-SnC 2o 4.
7. high energy density lithium ion electrokinetic cell according to claim 6, is characterized in that, described solubility tin salt is stannous chloride or stannous sulfate, and described Soluble oxalate salt is potassium oxalate, sodium oxalate or ammonium oxalate.
8. high energy density lithium ion electrokinetic cell according to claim 1, is characterized in that, described electrolyte comprises 3-5 kind functional additive, and the mass percent that every kind of functional additive accounts for electrolyte is W%, 1.0≤W≤5.0; The mass percent that the total amount of all functions additive accounts for electrolyte is N%, 5.0≤N≤15.
9. high energy density lithium ion electrokinetic cell according to claim 8, it is characterized in that, described functional additive is selected from any 3-5 kind in vinylene carbonate, propylene sulfite, fluorinated ethylene carbonate, vinylethylene carbonate and catechol carbonic ester.
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WO2016155315A1 (en) * 2015-03-31 2016-10-06 南通瑞翔新材料有限公司 High-nickel-type lithium ion secondary battery positive electrode material and preparation method therefor
CN106450454A (en) * 2016-10-19 2017-02-22 中航锂电（洛阳）有限公司 Electrolyte and lithium ion battery using electrolyte
CN108075179A (en) * 2016-11-18 2018-05-25 Sk新技术株式会社 Lithium secondary battery and its manufacturing method
CN108075178A (en) * 2016-11-18 2018-05-25 Sk新技术株式会社 Lithium secondary battery and its manufacturing method
CN108155375A (en) * 2016-12-06 2018-06-12 天津国安盟固利新材料科技股份有限公司 A kind of ternary cathode material of lithium ion battery and preparation method thereof
CN109713274A (en) * 2018-12-28 2019-05-03 天能电池(芜湖)有限公司 A kind of high-capacity lithium ion power battery and preparation method thereof
CN111082142A (en) * 2019-12-20 2020-04-28 中国电子科技集团公司第十八研究所 High-power and high-voltage-resistant lithium ion battery electrolyte and preparation method thereof

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016155315A1 (en) * 2015-03-31 2016-10-06 南通瑞翔新材料有限公司 High-nickel-type lithium ion secondary battery positive electrode material and preparation method therefor
CN106450454A (en) * 2016-10-19 2017-02-22 中航锂电（洛阳）有限公司 Electrolyte and lithium ion battery using electrolyte
CN108075179A (en) * 2016-11-18 2018-05-25 Sk新技术株式会社 Lithium secondary battery and its manufacturing method
CN108075178A (en) * 2016-11-18 2018-05-25 Sk新技术株式会社 Lithium secondary battery and its manufacturing method
CN108155375A (en) * 2016-12-06 2018-06-12 天津国安盟固利新材料科技股份有限公司 A kind of ternary cathode material of lithium ion battery and preparation method thereof
CN109713274A (en) * 2018-12-28 2019-05-03 天能电池(芜湖)有限公司 A kind of high-capacity lithium ion power battery and preparation method thereof
CN111082142A (en) * 2019-12-20 2020-04-28 中国电子科技集团公司第十八研究所 High-power and high-voltage-resistant lithium ion battery electrolyte and preparation method thereof

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Application publication date: 20140423