CN103618084A - Mixed positive material of lithium-ion power battery - Google Patents

Mixed positive material of lithium-ion power battery Download PDF

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CN103618084A
CN103618084A CN201310589616.2A CN201310589616A CN103618084A CN 103618084 A CN103618084 A CN 103618084A CN 201310589616 A CN201310589616 A CN 201310589616A CN 103618084 A CN103618084 A CN 103618084A
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lithium
ion
power cell
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anode material
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刘铁建
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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
    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • 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

Abstract

The invention belongs to the technical field of lithium-ion power batteries, and in particular relates to a mixed positive material of a high-capacity lithium-ion power battery. The mixed positive material comprises lithium iron phosphate A and a lithium nickel cobalt manganese ternary active substance B, wherein the surface of the A is coated with a polypyrrole layer; the median particle size of the A is smaller than or equal to 15 microns; the sizes of single-crystal particles of the B are greater than or equal to 1.0 microns; the surface of the B is coated with a metal fluoride layer. Compared with the prior art, the disadvantage of low compaction density caused by a ternary material is effectively overcome by reasonably optimizing the sizes of the single-crystal particles of the ternary material and the median particle size of the lithium iron phosphate, so that the mixed positive material has high compaction density; the surface of the lithium iron phosphate is coated with the polypyrrole layer and the surface of the ternary material is coated with the metal fluoride layer, so that the safety performance, the rate performance, the high-temperature cycling performance, the low-temperature performance and the safety performance of the lithium-ion power battery with the mixed positive material can be improved.

Description

A kind of lithium-ion-power cell blended anode material
Technical field
The invention belongs to lithium-ion-power cell technical field, relate in particular to a kind of high power capacity, lithium-ion-power cell blended anode material that fail safe is good.
Background technology
Along with the development of lithium-ion-power cell, people are more and more higher to the requirement of the flying power of its lithium ion battery, useful life, security performance and price etc.Positive electrode is one of key material of restriction lithium-ion-power cell cost performance, and the capacity and the fail safe that improve positive electrode are two main aspects that promote lithium-ion-power cell flying power.
LiFePO4 has been widely used in electrokinetic cell field, and it has the advantages such as high security and high cycle life.But LiFePO4 also exists obvious shortcoming, for example poorly conductive, lithium ion diffusion velocity are slow; During high power charging-discharging, actual specific capacity is low.In addition, LiFePO4 tap density is lower, generally can only reach 0.8-1.3; And use the poor performance at low temperatures of its electrokinetic cell of preparing.Generally, for single battery core, the capability retention in the time of its 0 ℃ is about 60-70%, is 40-55% in the time of-10 ℃, only has 20-40% in the time of-20 ℃.Such cryogenic property obviously can not meet the user demand of electrical source of power.
Lithium nickel cobalt manganese be ternary material tool have the following advantages: under 4.2V, actual reversible specific capacity can be up to 148～190mAh/g; Relatively abundant, the cheap and environmentally safe of nickel resources.Therefore, ternary material receives much attention in recent years, but this material also exists certain defect simultaneously: its actual compacted density is only 3.6g/cm 3, discharge voltage plateau is lower and have stronger water absorption; Particularly it is worth noting: Li in structure +and Ni 2+easily there is mixing, when causing active oxygen to be deviate from, make the decomposition of the easy catalytic electrolysis liquid of high price nickel ion, make the lithium ion battery of being made by ternary material when high temperature storage, produce a large amount of gas, worsen battery performance, especially for the lithium ion battery that adopts plastic-aluminum combined film as external packing, shell is soft, and the generation of gas will cause the sharply dilatancy of battery, bring serious potential safety hazard, thereby limit its use.
Summary of the invention
The object of the invention is to: for the deficiencies in the prior art, and provide a kind of, by LiFePO4 A and lithium nickel cobalt manganese, be the lithium-ion-power cell blended anode material that ternary active substance B mixes, this blended anode material has advantages of high power capacity, high security, good temperature characterisitic, cycle performance and high rate performance.
In order to achieve the above object, the present invention adopts following technical scheme:
A lithium-ion-power cell blended anode material, described positive electrode is that LiFePO4 A and lithium nickel cobalt manganese are the composite material of ternary active substance B, described lithium nickel cobalt manganese is that the expression formula of ternary active substance B is Li xni aco bm (1-a-b)o 2, 0.5≤x≤1.2 wherein; 0.33≤a≤1.0; 0≤b≤0.67; M is at least one in Al, Mn, Mg and Ba; The surface of described LiFePO4 A is coated with polypyrrole layer, the median particle diameter D50 of described LiFePO4 A is less than or equal to 15 μ m, described lithium nickel cobalt manganese is that the particle diameter of the monocrystal particle of ternary active substance B is more than or equal to 1.0 μ m, and described lithium nickel cobalt manganese is that the surface of ternary active substance B is coated with metal fluoride layer; Described lithium nickel cobalt manganese is that the mass ratio B/A of ternary active substance B and described LiFePO4 A is between 0.2 ~ 1.0.
The particle diameter (>=1.0 μ m) that increases the monocrystal particle of ternary material can improve the compacted density of ternary material effectively, and enhancing crushing resistance, after the LiFePO4 of less with median particle diameter D50 (≤15 μ m) mixes simultaneously, by sizes of balls, arrange in pairs or groups, effectively utilized the space between particle and particle, thereby compacted density is increased.
Surface is coated is at present for improving one of effective means of positive electrode cycle performance under high voltage, by being coated this conducting polymer composite with satisfactory electrical conductivity of polypyrrole layer on LiFePO4 surface, can greatly improve the conductivity of LiFePO4, improve the diffusion velocity of lithium ion, and then improve cycle performance and the high rate performance of LiFePO4.In addition,, because polypyrrole layer has high electro-chemical activity, therefore can improve the capacity of LiFePO4.The present invention is also by lithium nickel cobalt manganese being the coated metal fluoride layer that can be stable in HF in surface of ternary material, thereby can keep out the erosion of HF to ternary material, reduce the dissolving of metal ion, improve long-term cycle performance, high rate performance and the thermal stability of ternary material.
LiFePO4 A is to make to use the electrokinetic cell of composite material of the present invention to have the following advantages coordinating of ternary active substance B with lithium nickel cobalt manganese:
The one, operating voltage range is 2.75-4.2V, consistent with the operating voltage range of ternary material, but is obviously better than the operating voltage range of ferric phosphate lithium cell; The discharge voltage plateau of battery can reach 3.5V, lower than the 3.7V of ternary material, is still obviously better than the 3.3V of LiFePO4;
The 2nd, adopt the present invention as the lithium-ion-power cell of positive electrode, not only to keep the good high temperature cyclic performance of ferric phosphate lithium cell, and kept the good cryogenic property of ternary material, for single battery core, capability retention in the time of its 0 ℃ reaches more than 90%, while reaching 80% ,-20 ℃ in the time of-10 ℃, reach more than 60%;
The 3rd, adopt the present invention to there is good security performance and high rate performance as the lithium-ion-power cell of positive electrode, and there is higher compacted density.
As a kind of improvement of lithium-ion-power cell blended anode material of the present invention, the thickness of described polypyrrole layer is 0.1-5 μ m.If coating layer is too thin, little to the effect of the electric conductivity of raising LiFePO4; And if coating layer is too thick, can reduce again the content of active material, can reduce the energy density of battery.
As a kind of improvement of lithium-ion-power cell blended anode material of the present invention, the thickness of described polypyrrole layer is 0.5-3 μ m.
As a kind of improvement of lithium-ion-power cell blended anode material of the present invention, the thickness of described polypyrrole layer is 1 μ m.
As a kind of improvement of lithium-ion-power cell blended anode material of the present invention, described metal fluoride layer is LiF or AlF 3.Wherein be preferably LiF, because the amalgamation between itself and ternary material is better.
As a kind of improvement of lithium-ion-power cell blended anode material of the present invention, the thickness of described metal fluoride layer is 0.1-5 μ m.If coating layer is too thin, be not enough to suppress the side reaction between electrolyte and positive active material; If coating layer is too thick, greatly reduces reversible capacity and the discharge voltage plateau of positive active material, thereby reduced the energy density of battery.
As a kind of improvement of lithium-ion-power cell blended anode material of the present invention, the thickness of described metal fluoride layer is 0.5-3 μ m.
As a kind of improvement of lithium-ion-power cell blended anode material of the present invention, the thickness of described metal fluoride layer is 1 μ m.
As a kind of improvement of lithium-ion-power cell blended anode material of the present invention, the median particle diameter D50 of described LiFePO4 A is between 8 μ m ~ 15 μ m.
As a kind of improvement of lithium-ion-power cell blended anode material of the present invention, described lithium nickel cobalt manganese is that the particle diameter of monocrystal particle of ternary active substance B is between 1.0 μ m ~ 5.0 μ m.When the particle diameter of the monocrystal particle of ternary material is greater than 5.0 μ m, will greatly reduce the gram volume of material, therefore preferably the particle diameter of the monocrystal particle of ternary material is 1.0 ~ 5.0 μ m.
With respect to prior art, the present invention at least has the following advantages:
1) by the median particle diameter of the particle diameter of the single crystal grain of ternary material and LiFePO4 is carried out after reasonably optimizing, effectively improved the lower shortcoming of compacted density that ternary material brings, make mixed positive electrode there is higher compacted density.
2) by the coated polypyrrole layer in the surface at LiFePO4, and at the surface clad fluoride layer of ternary material, can improve and use the present invention as the security performance of the lithium-ion-power cell of positive electrode, high rate performance, high temperature cyclic performance, cryogenic property and security performance.
Embodiment
Lithium-ion-power cell provided by the invention adopts metal aluminum hull as battery container, and both positive and negative polarity pole piece combination electrolysis liquid sealing is in battery container, and the mode of both positive and negative polarity pole piece employing coiling or lamination is wrapped in barrier film in the middle of both positive and negative polarity pole piece.
Described anode pole piece comprise plus plate current-collecting body and electric conducting material, binding agent and of the present invention by LiFePO4 A and lithium nickel cobalt manganese, be the composite material that ternary active substance B forms.Wherein the content of electric conducting material and binding agent is 0～6wt.%, preferably 1%～4wt.%.
Described cathode pole piece comprises negative current collector and is coated in the negative electrode material layer on this negative current collector.Anticathode material layer of the present invention has no particular limits, generally include negative electrode active material, binding agent and conductive agent, wherein negative electrode active material can adopt carbon materials (as native graphite, Delanium, coke, active carbon, carbon fiber, carbon nanomaterial), nitride, silicon and silicide, tin-based oxide and stannide, lithium titanate, alloy material.Binding agent can be selected conventional negative pole binding agent, comprises one or more in polyvinyl alcohol, polytetrafluoroethylene, carboxymethyl cellulose, sodium carboxymethylcellulose, butadiene-styrene rubber (SBR).In general, the content of binding agent and conductive agent is 0～8wt.%, preferably 1%～4wt.%.
Described electrolyte comprises nonaqueous solvents and is dissolved in the electrolyte in this nonaqueous solvents, and electrolytical content is generally 0.5～2.0 mol/L.
The preferred chain acid esters of nonaqueous solvents in above-mentioned electrolyte and the mixed solvent of ring-type acid esters; Wherein chain acid esters can be selected from dimethyl carbonate, diethyl carbonate, ethyl propyl carbonic acid ester, diphenyl carbonate, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, dimethoxy-ethane, diethoxyethane with and fluorine-containing, sulfur-bearing and containing wherein a kind of or its mixture of the chain organosilane ester of unsaturated bond; Described ring-type acid esters can be selected from ethylene carbonate, propene carbonate, butylene, vinylene carbonate, gamma-butyrolacton, sultone with and fluorine-containing, sulfur-bearing or containing one of them or its mixture of the ring-type organosilane ester of unsaturated bond.
Described electrolyte can be selected LiPF 6, LiAsF 6, LiSbF 6, LiClO 4, LiBF 4, LiB (C 2h 5) 4, LiCF 3cO 2, LiCF 3sO 3, LiCH 3sO 3, LiC 4f 9s 3, Li (CF 3sO 3) 2one or more in N, LiCl, LiBr.
Below in conjunction with embodiment and comparative example, the present invention and beneficial effect thereof are done to carry out further detailed description, single embodiments of the present invention are not limited to this.
Embodiment 1
The present embodiment provides a kind of lithium-ion-power cell blended anode material, and positive electrode is LiFePO 4and LiNi 0.5co 0.2mn 0.3o 2composite material, wherein, LiFePO 4median particle diameter D50 be 10 μ m, LiNi 0.5co 0.2mn 0.3o 2the particle diameter of monocrystal particle be 1 μ m, LiNi 0.5co 0.2mn 0.3o 2and LiFePO 4mass ratio be 2:8, LiFePO 4surface be coated with the polypyrrole layer that thickness is 1 μ m, LiNi 0.5co 0.2mn 0.3o 2surface be coated with the LiF that thickness is 1 μ m.
Embodiment 2
As different from Example 1: LiFePO 4median particle diameter D50 be 12 μ m; LiNi 0.5co 0.2mn 0.3o 2the particle diameter of monocrystal particle be 2 μ m, the thickness of polypyrrole layer is 0.5 μ m, the thickness of LiF layer is 0.5 μ m.
Other is identical with embodiment 1, repeats no more here.
Embodiment 3
The present embodiment provides a kind of lithium-ion-power cell blended anode material, and positive electrode is LiFePO 4and LiNi 0.5co 0.2mg 0.3o 2composite material, wherein, LiFePO 4median particle diameter D50 be 15 μ m; LiNi 0.5co 0.2mg 0.3o 2the particle diameter of monocrystal particle be 3 μ m, LiCo 0.9mg 0.1o 2and LiNi 0.5co 0.2mg 0.3o 2mass ratio be 1:5.LiFePO 4surface be coated with the polypyrrole layer that thickness is 2 μ m, LiNi 0.5co 0.2mg 0.3o 2surface be coated with the AlF that thickness is 2 μ m 3.
Embodiment 4
The present embodiment provides a kind of lithium-ion-power cell blended anode material, and positive electrode is LiFePO 4and LiNi 0.4co 0.3al 0.3o 2composite material, LiFePO wherein 4median particle diameter D50 be 8 μ m; LiNi 0.4co 0.3al 0.3o 2the particle diameter of monocrystal particle be 5 μ m, Li 1.1co 0.8mg 0.1ti 0.1o 2and LiNi 0.4co 0.3al 0.3o 2mass ratio be 3:10.LiFePO 4surface be coated with the polypyrrole layer that thickness is 3 μ m, LiNi 0.4co 0.3al 0.3o 2surface be coated with the AlF that thickness is 3 μ m 3.
Embodiment 5
The present embodiment provides a kind of lithium-ion-power cell blended anode material, and positive electrode is LiFePO 4and LiNi 0.6co 0.2mg 0.2o 2composite material, wherein, LiFePO 4median particle diameter D50 be 15 μ m; LiNi 0.6co 0.2mg 0.2o 2the particle diameter of monocrystal particle be 3 μ m, LiFePO 4and LiNi 0.6co 0.2mg 0.2o 2mass ratio be 1:2.LiFePO 4surface be coated with the polypyrrole layer that thickness is 5 μ m, LiNi 0.6co 0.2mg 0.2o 2surface be coated with the AlF that thickness is 5 μ m 3.
Embodiment 6
The present embodiment provides a kind of lithium-ion-power cell blended anode material, and positive electrode is LiFePO 4and LiNi 0.6co 0.2mg 0.2o 2composite material, wherein, LiFePO 4median particle diameter D50 be 15 μ m; LiNi 0.6co 0.2mg 0.2o 2the particle diameter of monocrystal particle be 3 μ m, LiFePO 4and LiNi 0.6co 0.2mg 0.2o 2mass ratio be 1:1.LiFePO 4surface be coated with the polypyrrole layer that thickness is 0.1 μ m, LiNi 0.6co 0.2mg 0.2o 2surface be coated with the AlF that thickness is 0.1 μ m 3.
Embodiment 7
The present embodiment provides a kind of lithium-ion-power cell blended anode material, and positive electrode is LiFePO 4and Li 0.6ni 0.8co 0.1mn 0.1o 2composite material, wherein, LiFePO 4median particle diameter D50 be 15 μ m; Li 0.6ni 0.8co 0.1mn 0.1o 2the particle diameter of monocrystal particle be 3 μ m, LiFePO 4and LiNi 0.6co 0.2mg 0.2o 2mass ratio be 3:5.LiFePO 4surface be coated with the polypyrrole layer that thickness is 4 μ m, Li 0.6ni 0.8co 0.1mn 0.1o 2surface be coated with the LiF that thickness is 4 μ m.
Embodiment 8
The present embodiment provides a kind of lithium-ion-power cell blended anode material, and positive electrode is LiFePO 4and Li 0.8ni 0.7co 0.1mn 0.1al 0.1o 2composite material, wherein, LiFePO 4median particle diameter D50 be 15 μ m; Li 0.8ni 0.7co 0.1mn 0.1al 0.1o 2the particle diameter of monocrystal particle be 3 μ m, LiFePO 4and Li 0.8ni 0.7co 0.1mn 0.1al 0.1o 2mass ratio be 4:5.LiFePO 4surface be coated with the polypyrrole layer that thickness is 2 μ m, Li 0.8ni 0.7co 0.1mn 0.1al 0.1o 2surface be coated with the LiF that thickness is 3 μ m.
Comparative example 1
As different from Example 1: LiFePO 4average grain diameter D50 be 15 μ m; LiNi 0.5co 0.2mn 0.3o 2monocrystal particle be 3 μ m, LiFePO 4and LiNi 0.5co 0.2mn 0.3o 2surface all coated.
The blended anode material of embodiment 1 to 8 and comparative example 1 and bonding agent (as PVDF) and conductive agent (as conductive carbon) are added in solvent (as 1-METHYLPYRROLIDONE), make anode sizing agent, then anode sizing agent is coated on plus plate current-collecting body, make anode pole piece, and be assembled into lithium-ion-power cell with cathode pole piece, barrier film and electrolyte, to adopt the lithium-ion-power cell of the blended anode material of embodiment 1 to 8 to be numbered S1-S8, will adopt the lithium ion battery of the blended anode material of comparative example 1 to be numbered D1.
Performance test: carry out following test to being numbered the lithium-ion-power cell of S1-S4 and D1:
1, anode pole piece compacted density test.
To adopt the anode pole piece of the blended anode material of embodiment 1 to 4 and comparative example 1 to carry out after double spread, cutting area be 1540.25mm 2double spread disk, take its quality and be designated as M (g).Then, under the pressure of 90 ± 25T and constant speed, the anode pole piece of double spread is colded pressing, after colding pressing, with the thickness of miking pole piece, be designated as L (mm).The compacted density PD of anode pole piece can be expressed as:
PD=M/ (1540.25 * (L-R)) * 1000 (g/cm 3), wherein, the thickness that R is collector (mm).
2, battery performance test.
To being numbered the lithium ion battery of S1-S4 and D1, carry out charge-discharge test, the initial capacity of battery relatively, test condition: first battery is changed into, at 45 ℃ first with 0.01C constant current charge to 3.4V, then with 0.2C constant current charge to 3.8V; Then at normal temperatures, with 0.2C size of current constant current charge, to 4.2V, then constant voltage is to 0.05C, after standing 5min, with 0.2C, is discharged to 3.0V, records discharge capacity.
3,25 ℃ of cycle performance tests of battery.
To being numbered the lithium ion battery of S1-S4 and D1, carry out cycle performance test: at 25 ℃, to 4.2V, constant voltage is to 0.05C with 1C constant current charge, and after standing 30min, to 3.0V, standing 30min, circulates 400 weeks successively with 1C constant-current discharge.Discharge capacity * 100% of discharge capacity/the first of the capability retention of battery=400th week week.
4,60 ℃ of cycle performance tests of battery.
To being numbered the lithium ion battery of S1-S4 and D1, carry out cycle performance test: at 60 ℃, to 4.2V, constant voltage is to 0.05C with 1C constant current charge, and after standing 30min, to 3.0V, standing 30min, circulates 400 weeks successively with 1C constant-current discharge.Discharge capacity * 100% of discharge capacity/the first of the capability retention of battery=400th week week.
Table 1: the performance test results that is numbered the lithium-ion-power cell of S1-S4 and D1.
Figure 685389DEST_PATH_IMAGE002
As can be seen from Table 1, the particle diameter that is the single crystal grain of ternary active substance B along with median particle diameter D50 and the lithium nickel cobalt manganese of LiFePO4 A constantly increases, the compacted density of anode pole piece improves constantly, the high-temperature storage performance of battery is also significantly improved simultaneously, but the gram volume of battery presents continuous downward trend.This is mainly because after particle change greatly, the transmission path of lithium ion in positive electrode is elongated, thereby makes polarization larger.When the median particle diameter D50 of LiFePO4 A is that 15 μ m and lithium nickel cobalt manganese are the particle diameter of the single crystal grain of ternary active substance B while being 3.0 μ m, the chemical property of battery and the compacted density of anode pole piece reach the optimum value on comprehensive.
Adopt the lithium-ion-power cell of positive electrode of the present invention to there is higher capacity, compacted density, discharge platform and cycle performance.
To being numbered the lithium-ion-power cell of S5-S8, test as follows:
4, security performance test: get respectively 20 lithium-ion-power cells that are numbered S5-S8 and D1 and carry out acupuncture, extruding, heavy impact, overcharge test and cross and put test.Wherein, overcharge test be: under normal temperature, with 1.0C current charges, to 10V, maintain 2 hours, record battery core and whether smolder, on fire, blast, acquired results is in Table 2.
5, low temperature discharge volume test: at-20 ℃, to being numbered the lithium ion battery of S5-S8 and D1, carry out charge-discharge test, compare the initial capacity of battery, test condition: first battery is changed into, at normal temperatures first with 0.01C constant current charge to 3.4V, then with 0.2C constant current charge to 3.8V; Then at-20 ℃, with 0.2C size of current constant current charge, to 4.2V, then constant voltage is to 0.05C, after standing 5min, with 0.2C, is discharged to 3.0V, records discharge capacity, and acquired results is in Table 2.
Table 2: the performance test results that is numbered the lithium-ion-power cell of S5-S8 and D1.
Figure 497336DEST_PATH_IMAGE002
As can be seen from Table 2: adopt the lithium-ion-power cell of positive electrode of the present invention to there is better security performance and cryogenic property.
In view of those skilled in the art in the invention can also carry out suitable change and modification to above-mentioned execution mode; therefore; the present invention is not limited to embodiment disclosed and described above, within also should falling into the protection range of claim of the present invention to modifications and changes more of the present invention.In addition,, although used some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.

Claims (10)

1. a lithium-ion-power cell blended anode material, described positive electrode is that LiFePO4 A and lithium nickel cobalt manganese are the composite material of ternary active substance B, described lithium nickel cobalt manganese is that the expression formula of ternary active substance B is Li xni aco bm (1-a-b)o 2, 0.5≤x≤1.2 wherein; 0.33≤a≤1.0; 0≤b≤0.67; M is at least one in Al, Mn, Mg and Ba; It is characterized in that: the surface of described LiFePO4 A is coated with polypyrrole layer, the median particle diameter D50 of described LiFePO4 A is less than or equal to 15 μ m, described lithium nickel cobalt manganese is that the particle diameter of the monocrystal particle of ternary active substance B is more than or equal to 1.0 μ m, and described lithium nickel cobalt manganese is that the surface of ternary active substance B is coated with metal fluoride layer; Described lithium nickel cobalt manganese is that the mass ratio B/A of ternary active substance B and described LiFePO4 A is between 0.2 ~ 1.0.
2. lithium-ion-power cell blended anode material according to claim 1, is characterized in that: the thickness of described polypyrrole layer is 0.1-5 μ m.
3. lithium-ion-power cell blended anode material according to claim 2, is characterized in that: the thickness of described polypyrrole layer is 0.5-3 μ m.
4. lithium-ion-power cell blended anode material according to claim 3, is characterized in that: the thickness of described polypyrrole layer is 1 μ m.
5. lithium-ion-power cell blended anode material according to claim 1, is characterized in that: described metal fluoride layer is LiF or AlF3.
6. lithium-ion-power cell blended anode material according to claim 5, is characterized in that: the thickness of described metal fluoride layer is 0.1-5 μ m.
7. lithium-ion-power cell blended anode material according to claim 6, is characterized in that: the thickness of described metal fluoride layer is 0.5-3 μ m.
8. lithium-ion-power cell blended anode material according to claim 7, is characterized in that: the thickness of described metal fluoride layer is 1 μ m.
9. lithium-ion-power cell blended anode material according to claim 1, is characterized in that: the median particle diameter D50 of described LiFePO4 A is between 8 μ m ~ 15 μ m.
10. lithium-ion-power cell blended anode material according to claim 1, is characterized in that: described lithium nickel cobalt manganese is that the particle diameter of monocrystal particle of ternary active substance B is between 1.0 μ m ~ 5.0 μ m.
CN201310589616.2A 2013-11-21 2013-11-21 Mixed positive material of lithium-ion power battery Pending CN103618084A (en)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104112851A (en) * 2014-07-18 2014-10-22 厦门太和动力电源科技有限公司 Surface coating method for ternary positive material of lithium ion battery
CN106935829A (en) * 2017-03-30 2017-07-07 上海动力储能电池系统工程技术有限公司 A kind of method for strengthening lithium ion battery lithium titanate material low-temperature characteristics
CN107910507A (en) * 2017-10-27 2018-04-13 天津市捷威动力工业有限公司 A kind of tertiary cathode material
CN109461964A (en) * 2017-09-06 2019-03-12 宁德时代新能源科技股份有限公司 Lithium ion secondary battery
CN109713225A (en) * 2017-10-26 2019-05-03 宁德时代新能源科技股份有限公司 Lithium ion secondary battery
CN109713237A (en) * 2017-10-26 2019-05-03 宁德时代新能源科技股份有限公司 Lithium ion secondary battery
CN110676428A (en) * 2019-10-17 2020-01-10 朱虎 Preparation method of mixed anode for lithium ion battery
CN111430694A (en) * 2020-04-09 2020-07-17 盛蕾 Mixing method of composite anode slurry
WO2021109080A1 (en) * 2019-12-05 2021-06-10 宁德时代新能源科技股份有限公司 Lithium ion battery, positive electrode sheet for lithium ion battery, and device
CN112952050A (en) * 2019-12-11 2021-06-11 广州汽车集团股份有限公司 Positive active material, positive pole piece, lithium ion soft package battery cell, lithium ion battery pack and application thereof
CN114824280A (en) * 2022-06-27 2022-07-29 蚂蚁新能源科技(天津)有限公司 Composite positive electrode material for lithium ion battery dry-method electrode and preparation method and application thereof
CN115172698A (en) * 2022-07-18 2022-10-11 江苏正力新能电池技术有限公司 Positive electrode material, positive plate and secondary battery
WO2023046066A1 (en) * 2021-09-24 2023-03-30 比亚迪股份有限公司 Battery positive electrode material and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101154727A (en) * 2007-09-14 2008-04-02 中南大学 Coating method of porous clad material for effectively improving rate performance of lithium nickel cobalt manganese oxygen
CN101295780A (en) * 2007-04-28 2008-10-29 深圳市比克电池有限公司 Anode active material composition of lithium ion secondary battery and battery
CN101478039A (en) * 2009-02-05 2009-07-08 上海交通大学 Preparation for polypyrole coated lithium iron phosphate
CN102449822A (en) * 2009-05-27 2012-05-09 株式会社Lg化学 Positive electrode active material, and positive electrode and lithium secondary battery comprising same
CN102473957A (en) * 2009-07-24 2012-05-23 安维亚系统公司 Lithium ion batteries with long cycling performance
CN103022499A (en) * 2012-12-03 2013-04-03 东莞新能源科技有限公司 Mixed positive-pole material for lithium ion battery
WO2013129182A1 (en) * 2012-02-29 2013-09-06 新神戸電機株式会社 Lithium-ion cell

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101295780A (en) * 2007-04-28 2008-10-29 深圳市比克电池有限公司 Anode active material composition of lithium ion secondary battery and battery
CN101154727A (en) * 2007-09-14 2008-04-02 中南大学 Coating method of porous clad material for effectively improving rate performance of lithium nickel cobalt manganese oxygen
CN101478039A (en) * 2009-02-05 2009-07-08 上海交通大学 Preparation for polypyrole coated lithium iron phosphate
CN102449822A (en) * 2009-05-27 2012-05-09 株式会社Lg化学 Positive electrode active material, and positive electrode and lithium secondary battery comprising same
CN102473957A (en) * 2009-07-24 2012-05-23 安维亚系统公司 Lithium ion batteries with long cycling performance
WO2013129182A1 (en) * 2012-02-29 2013-09-06 新神戸電機株式会社 Lithium-ion cell
CN103022499A (en) * 2012-12-03 2013-04-03 东莞新能源科技有限公司 Mixed positive-pole material for lithium ion battery

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104112851A (en) * 2014-07-18 2014-10-22 厦门太和动力电源科技有限公司 Surface coating method for ternary positive material of lithium ion battery
CN106935829A (en) * 2017-03-30 2017-07-07 上海动力储能电池系统工程技术有限公司 A kind of method for strengthening lithium ion battery lithium titanate material low-temperature characteristics
CN109461964A (en) * 2017-09-06 2019-03-12 宁德时代新能源科技股份有限公司 Lithium ion secondary battery
CN109461964B (en) * 2017-09-06 2021-06-08 宁德时代新能源科技股份有限公司 Lithium ion secondary battery
CN109713225A (en) * 2017-10-26 2019-05-03 宁德时代新能源科技股份有限公司 Lithium ion secondary battery
CN109713237A (en) * 2017-10-26 2019-05-03 宁德时代新能源科技股份有限公司 Lithium ion secondary battery
CN107910507A (en) * 2017-10-27 2018-04-13 天津市捷威动力工业有限公司 A kind of tertiary cathode material
CN110676428B (en) * 2019-10-17 2020-12-15 泰州纳新新能源科技有限公司 Preparation method of mixed anode for lithium ion battery
CN110676428A (en) * 2019-10-17 2020-01-10 朱虎 Preparation method of mixed anode for lithium ion battery
WO2021109080A1 (en) * 2019-12-05 2021-06-10 宁德时代新能源科技股份有限公司 Lithium ion battery, positive electrode sheet for lithium ion battery, and device
CN112952050A (en) * 2019-12-11 2021-06-11 广州汽车集团股份有限公司 Positive active material, positive pole piece, lithium ion soft package battery cell, lithium ion battery pack and application thereof
CN111430694A (en) * 2020-04-09 2020-07-17 盛蕾 Mixing method of composite anode slurry
WO2023046066A1 (en) * 2021-09-24 2023-03-30 比亚迪股份有限公司 Battery positive electrode material and application thereof
CN114824280A (en) * 2022-06-27 2022-07-29 蚂蚁新能源科技(天津)有限公司 Composite positive electrode material for lithium ion battery dry-method electrode and preparation method and application thereof
CN114824280B (en) * 2022-06-27 2022-09-06 蚂蚁新能源科技(天津)有限公司 Composite positive electrode material for lithium ion battery dry-method electrode and preparation method and application thereof
CN115172698A (en) * 2022-07-18 2022-10-11 江苏正力新能电池技术有限公司 Positive electrode material, positive plate and secondary battery

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