CN103794781A - Lithium battery as well as preparation method thereof - Google Patents

Lithium battery as well as preparation method thereof Download PDF

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CN103794781A
CN103794781A CN201410069175.8A CN201410069175A CN103794781A CN 103794781 A CN103794781 A CN 103794781A CN 201410069175 A CN201410069175 A CN 201410069175A CN 103794781 A CN103794781 A CN 103794781A
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lithium
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rich manganese
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郭伟
戴思琦
慈云祥
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Beijing National Battery Technology Co Ltd
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Beijing National Battery Technology 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
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/04—Construction or manufacture in general
    • H01M10/0404—Machines for assembling 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
    • H01M10/052—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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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Abstract

The invention provides a lithium battery as well as a preparation method thereof. A battery system consists of a positive electrode piece, a negative electrode piece, electrolyte, a diaphragm and an outer package, wherein a lithium-rich manganese base is adopted as a positive electrode active substance, and the formula of the active substance is zLi2MnO3.(1-z)Li(Ni0.6Mn0.2Co0.2)O2, wherein z is more than or equal to 0.5 and less than or equal to 0.7, or the formula of the active substance is xLi2MnO3.(1-x)Li(Ni(0.7-y)Mn0.15Co0.15My)O2, wherein x is more than or equal to 0.4 and is less than or equal to 0.7, M is a doped element, and y is more than 0.01 and less than 0.05; a silicon material is adopted as a negative electrode active substance. Because the lithium-rich manganese base and the silicon material both have relative high capacity in the field of positive and negative electrode materials of lithium batteries, the battery has high capacity and high energy density exceeding 300Wh/kg, and with the advantages, the battery can be well applied to minitype and power battery systems in the future.

Description

A kind of lithium battery and preparation method thereof
Technical field
The present invention relates to a kind of lithium battery and preparation method thereof, relate in particular to employing lithium-rich manganese-based as cell positive material, silicon based material is as the lithium ion battery with high energy density of negative pole.
Background technology
Along with the continuous renewal of modern electronic product is regenerated, new-energy automobile is more and more higher to the requirement of distance travelled, and each side factor all forces us to develop to have the more battery system of high-energy-density the more efficient energy is provided.In " energy-conservation and new-energy automobile estate planning ", require electrokinetic cell energy density will reach 300Wh/Kg before the year two thousand twenty.This target relatively, the employing LiCoO of existing industrialization 2the small-sized lithium electricity of Soft Roll of made is also only only less than the energy density of 250Wh/kg, and therefore, if want to reach above-mentioned target, we need to adopt the lithium electricity system of renewal to make battery so.
What in lithium electricity positive electrode, capacity was the highest is undoubtedly lithium-rich manganese-based solid-solution material, and molecular formula is xLi 2mnO 3(1-x) LiMO 2, the specific discharge capacity of this material can approach 300mAh/g, well beyond other materials, improves in recent years because each corporate facility also makes this material have than before in the defects such as cycle performance, rate energy significantly to the research and development energetically of this material.Aspect negative pole, silicium cathode material becomes the focus that Ge great Battery Plant develops in recent years, this materials theory capacity can arrive 4200mAh/g, 10 times of existing graphite cathode material capacity, adopt this negative pole to use in lithium ion battery and will compare and adopt the battery of conventional graphite negative pole system to increase and exceed 30% in bulk density, mass energy density increases by 10%～30%.Under above-mentioned both positive and negative polarity system, the energy content of battery density of made will be well beyond existing battery system.
Therefore, we are take lithium-rich manganese-based material as anodal, silicon based material be negative pole as research emphasis, exploitation has the more lithium ion battery of high-energy-density.
Summary of the invention
The present invention proposes a kind of lithium battery and preparation method thereof, to solve the LiCoO of existing industrialization 2the lithium battery energy density of made is only less than the technological deficiency of 250Wh/kg.
For achieving the above object, the present invention proposes a kind of lithium battery, adopts lithium-rich manganese-based material as positive pole, adopts silicon based material as negative pole.
Wherein, described lithium-rich manganese-based material molecule formula is zLi 2mnO 3(1-z) Li (Ni 0.6mn 0.2co 0.2) O 2, wherein 0.5≤z≤0.7, or xLi 2mnO 3(1-x) Li (Ni 0.7- ymn 0.15co 0.15m y) O 2, 0.4≤x≤0.7, M is doped chemical, 0.01<y<0.05, M is one or both in Ti, B, Al, Mg.
Wherein, described lithium-rich manganese-based material is selected from 0.5Li 2mnO 30.5Li (Ni 0.6mn 0.2co 0.2) O 2, 0.6Li 2mnO 30.4Li (Ni 0.6mn 0.2co 0.2) O 2, 0.7Li 2mnO 30.3Li (Ni 0.6mn 0.2co 0.2) O 2, 0.4Li 2mnO 30.6Li (Ni 0.65mn 0.15co 0.15ti 0.05) O 2, 0.5Li 2mnO 30.5Li (Ni 0.68mn 0.15co 0.15ti 0.02) O 2, 0.6Li 2mnO 30.4Li (Ni 0.6985mn 0.15co 0.15ti 0.0015) O 2, 0.6Li 2mnO 30.4Li (Ni 0.68mn 0.15co 0.15b 0.02) O 2, 0.7Li 2mnO 30.3Li (Ni 0.697mn 0.15co 0.15al 0.003) O 2or 0.7Li 2mnO 30.3Li (Ni 0.695mn 0.15co 0.15al 0.005) O 2
Wherein, described lithium-rich manganese-based material is coated through metal oxide, and in described metal oxide, metallic element is one or both mixtures in V, Mn, Mg or Al, and described metal oxide covering amount is 1%～6% of described lithium-rich manganese-based material molal quantity.
Wherein, described silicon is that negative material is Si-C composite material, silicon nanowires, nano-tube or the coated nano-tube of process carbon, and in described Si-C composite material, the content of silicon accounts for 4%～20% of total material weight ratio.
And for achieving the above object, the present invention proposes a kind of manufacture method of lithium battery, the lithium-rich manganese-based material of anodal employing is made, and negative pole adopts silicon based material to make.
And the manufacture method of above-mentioned lithium battery comprises the steps:
Step 1: prepare pole piece slurry: the lithium-rich manganese-based material of anodal employing, molecular formula is zLi 2mnO 3(1-z) Li (Ni 0.6mn 0.2co 0.2) O 2, wherein 0.5≤z≤0.7, or xLi 2mnO 3(1-x) Li (Ni 0.7-ymn 0.15co 0. 15m y) O 2, 0.4≤x≤0.7, M is doped chemical, 0.01<y<0.05, M is one or both in Ti, B, Al, Mg, and positive electrode, conductive agent, binding agent, solvent are joined in batch mixer and carry out batch mixing, obtains anode sizing agent; Negative pole adopts silicon based material, and described silicon based material, conductive agent, binding agent and solvent are added in mixing hollander and carry out batch mixing, obtains cathode size;
Step 2: positive and negative electrode pole piece preparation: anode sizing agent is coated on plus plate current-collecting body, with 110 ℃～150 degrees Celsius dry oven dry, then carries out roller compaction in baking oven, compacted density is controlled at 2.4～3.1g/cm 3, obtain anode pole piece; Cathode size is coated on negative current collector, in baking oven, dries with 90～110 ℃, carry out pair roller roll extrusion, compacted density is at 1.2～1.7g/cm 3, obtain cathode pole piece;
Step 3: assembled battery: adopt stacked or takeup type to be assembled into battery core according to positive plate, barrier film and negative plate successively order pole piece, the anode pole piece lug of battery core and cathode pole piece lug are welded together respectively, and battery core is packed in battery container;
Step 4: fluid injection, change into: inject the electrolyte in battery, and sealing, the battery assembling is carried out to partial volume and change into and obtain final battery.
Wherein, described in described step 1, lithium-rich manganese-based material is selected from 0.5Li 2mnO 30.5Li (Ni 0.6mn 0.2co 0. 2) O 2, 0.6Li 2mnO 30.4Li (Ni 0.6mn 0.2co 0.2) O 2, 0.7Li 2mnO 30.3Li (Ni 0.6mn 0.2co 0.2) O 2, 0.4Li 2mnO 30.6Li (Ni 0.65mn 0.15co 0.15ti 0.05) O 2, 0.5Li 2mnO 30.5Li (Ni 0.68mn 0.15co 0.15ti 0.02) O 2, 0.6Li 2mnO 30.4Li (Ni 0.6985mn 0.15co 0.15ti 0.0015) O 2, 0.6Li 2mnO 30.4Li (Ni 0.68mn 0.15co 0.15b 0.02) O 2, 0.7Li 2mnO 30.3Li (Ni 0.697mn 0.15co 0.15al 0.003) O 2or 0.7Li 2mnO 30.3Li (Ni 0.695mn 0.15co 0.15al 0.005) O 2.
Wherein, lithium-rich manganese-based material zLi described in described step 1 2mnO 3(1-z) Li (Ni 0.6mn 0.2co 0.2) O 2, wherein 0.5≤z≤0.7, or xLi 2mnO 3(1-x) Li (Ni 0.7-ymn 0.15co 0.15m y) O 2coated through metal oxide, in described metal oxide, metallic element is one or both mixtures in V, Mn, Mg, Al, and the covering amount of described metal oxide is 1%～6% of lithium-rich manganese-based material molal quantity.
Wherein, in described step 1, conductive agent described in described anode sizing agent is one or more mixtures in conductive black, electrically conductive graphite, acetylene black, carbon nano-tube; Described adhesive is one or more mixtures in PVDF, CMC, PVP, SBR, PAN; Described solvent is one or more mixtures in 1-METHYLPYRROLIDONE, N-N-dimethyl pyrrolidone, dimethyl formamide, absolute ethyl alcohol, acetone; Each constituent content in described anode sizing agent is: described positive electrode 88%～96%, and described conductive agent 1%～6%, described binding agent 1%～6%, the amount of the described solvent adding is to make the solid content of slurry 40%～60%.
Wherein, silicon based material described in described step 1 is Si-C composite material, silicon nanowires, nano-tube or the coated nano-tube of process carbon, and wherein in Si-C composite material, the content of silicon accounts for 4%～20% of total material weight ratio; Conductive agent described in described cathode size is one or more mixtures in graphite, carbon black, acetylene black, carbon fiber, carbon nano-tube; Described adhesive is one or more mixtures in styrene butadiene rubbers, Kynoar, polyvinyl alcohol, sodium carboxymethylcellulose, acrylonitrile, and described solvent is one or both mixtures in water, 1-METHYLPYRROLIDONE or N-N-dimethyl pyrrolidone; Each constituent content in described cathode size is: described silicon based material 90%～96%, and described conductive agent 1%～5%, described binding agent 1%～6%, the amount of the described solvent adding makes the solid content of slurry 35%～50%.
Wherein, the coated face density of anode sizing agent described in described step 2 is 15 × 10 -3g/cm 2～22 × 10 -3g/cm 2, the coated face density of described cathode size is 4 × 10 -3g/cm 2～12 × 10 -3g/cm 2.
Make lithium ion battery with high energy density, this battery is compared the prepared battery system of traditional handicraft and is had higher energy density, and energy content of battery density can reach 300Wh/kg.Be applicable to small-sized and electrokinetic cell needs.
Lithium battery positive pole active substance of the present invention adopts lithium-rich manganese-based material and negative electrode active material to adopt silicon based material, prepared lithium battery is compared the prepared battery system of traditional handicraft and is had higher energy density, energy content of battery density can reach 300Wh/kg, is applicable to small-sized and electrokinetic cell needs.In addition, doping metals in the application's anode material of lithium battery, also can be coated anodal material surface, has further improved the energy density of lithium battery.
Accompanying drawing explanation
Fig. 1 is the application's lithium battery preparation method process sequence diagram;
Fig. 2 is battery first charge-discharge curve in embodiment 1.
Embodiment
It is negative material that the present invention adopts lithium-rich manganese-based anode material and silicon, has promoted lithium ion battery energy density.
For achieving the above object, the present invention proposes a kind of lithium battery, adopts lithium-rich manganese-based material as positive pole, adopts silicon based material as negative pole.
Wherein, described lithium-rich manganese-based material molecule formula is zLi 2mnO 3(1-z) Li (Ni 0.6mn 0.2co 0.2) O 2, wherein 0.5≤z≤0.7 or xLi 2mnO 3(1-x) Li (Ni 0.7-ymn 0.15co 0.15m y) O 2, 0.4≤x≤0.7, M is doped chemical, 0.01<y<0.05, M is one or both in Ti, B, Al, Mg.
Wherein, described lithium-rich manganese-based material is selected from 0.5Li 2mnO 30.5Li (Ni 0.6mn 0.2co 0.2) O 2, 0.6Li 2mnO 30.4Li (Ni 0.6mn 0.2co 0.2) O 2, 0.7Li 2mnO 30.3Li (Ni 0.6mn 0.2co 0.2) O 2, 0.4Li 2mnO 30.6Li (Ni 0.65mn 0.15co 0.15ti 0.05) O 2, 0.5Li 2mnO 30.5Li (Ni 0.68mn 0.15co 0.15ti 0.02) O 2, 0.6Li 2mnO 30.4Li (Ni 0.6985mn 0.15co 0.15ti 0.0015) O 2, 0.6Li 2mnO 30.4Li (Ni 0.68mn 0.15co 0.15b 0.02) O 2, 0.7Li 2mnO 30.3Li (Ni 0.697mn 0.15co 0.15al 0.003) O 2or 0.7Li 2mnO 30.3Li (Ni 0.695mn 0.15co 0.15al 0.005) O 2.
Wherein, described lithium-rich manganese-based material is coated through metal oxide, and in described metal oxide, metallic element is one or both mixtures in V, Mn, Mg or Al, and described metal oxide covering amount is 1%～6% of described lithium-rich manganese-based material molal quantity.
Wherein, described silicon is that negative material is Si-C composite material, silicon nanowires, nano-tube or the coated nano-tube of process carbon, and in described Si-C composite material, the content of silicon accounts for 4%～20% of total material weight ratio.
And for achieving the above object, the present invention proposes a kind of manufacture method of lithium battery, the lithium-rich manganese-based material of anodal employing is made, and negative pole adopts silicon based material to make.
And the manufacture method of above-mentioned lithium battery comprises the steps (as Fig. 1):
Step 1: prepare pole piece slurry: the lithium-rich manganese-based material of anodal employing, molecular formula is zLi 2mnO 3(1-z) Li (Ni 0.6mn 0.2co 0.2) O 2, wherein 0.5≤z≤0.7 or xLi 2mnO 3(1-x) Li (Ni 0.7- ymn 0.15co 0.1 5m y) O 2, 0.4≤x≤0.7, M is doped chemical, 0.01<y<0.05, M is one or both in Ti, B, Al, Mg, and positive electrode, conductive agent, binding agent, solvent are joined in batch mixer and carry out batch mixing, obtains anode sizing agent; Negative pole adopts silicon based material, and described silicon based material, conductive agent, binding agent and solvent are added in mixing hollander and carry out batch mixing, obtains cathode size;
Step 2: positive and negative electrode pole piece preparation: anode sizing agent is coated on plus plate current-collecting body, with 110 ℃～150 degrees Celsius dry oven dry, then carries out roller compaction in baking oven, compacted density is controlled at 2.4～3.1g/cm 3, obtain anode pole piece; Cathode size is coated on negative current collector, in baking oven, dries with 90～110 ℃, carry out pair roller roll extrusion, compacted density is at 1.2～1.7g/cm 3, obtain cathode pole piece;
Step 3: assembled battery: pole piece is cut into the size needing, adopt stacked or takeup type to be assembled into battery core according to positive plate, barrier film and negative plate successively order pole piece, the anode pole piece lug of battery core and cathode pole piece lug are welded together respectively, and battery core is packed in battery container;
Step 4: fluid injection, change into: inject the electrolyte in battery, and sealing, the battery assembling is carried out to partial volume and change into and obtain final battery.
According to preparation method provided by the present invention, step 1: described in lithium-rich manganese-based chemical equation be zLi 2mnO 3(1-z) Li (Ni 0.6mn 0.2co 0.2) O 2, wherein 0.5≤z≤0.7 or xLi 2mnO 3(1-x) Li (Ni 0. 7-ymn 0.15co 0.15m y) O 2, 0.4≤x≤0.7, M is doped chemical, 0.01<y<0.05, M is one or both in Ti, B, Al, Mg.More preferably: 0.5Li 2mnO 30.5Li (Ni 0.6mn 0.2co 0.2) O 2, 0.6Li 2mnO 30.4Li (Ni 0.6mn 0.2co 0.2) O 2, 0.7Li 2mnO 30.3Li (Ni 0.6mn 0.2co 0.2) O 2, 0.4Li 2mnO 30.6Li (Ni 0.65mn 0.15co 0. 15ti 0.05) O 2, 0.5Li 2mnO 30.5Li (Ni 0.68mn 0.15co 0.15ti 0.02) O 2, 0.6Li 2mnO 30.4Li (Ni 0.6985mn 0.15co 0.15ti 0.0015) O 2, 0.6Li 2mnO 30.4Li (Ni 0.68mn 0.15co 0.1 5b 0.02) O 2, 0.7Li 2mnO 30.3Li (Ni 0.697mn 0.15co 0.15al 0.003) O 2or 0.7Li 2mnO 30.3Li (Ni 0.695mn 0.15co 0.15al 0.005) O 2.
According to preparation method provided by the present invention, lithium-rich manganese-based zLi described in step 1 2mnO 3(1-z) Li (Ni 0.6mn 0.2co 0.2) O 2, wherein 0.5≤z≤0.7 or xLi 2mnO 3(1-x) Li (Ni 0.7-ymn 0.15co 0.15m y) O2,0.4≤x≤0.7, wherein M is doping metals, can be one or both in Ti, B, Al, Mg, 0≤y≤0.05.
According to preparation method provided by the present invention, lithium-rich manganese-based material zLi described in step 1 2mnO 3(1-z) Li (Ni 0.6mn 0.2co 0.2) O2, wherein 0.5≤z≤0.7 or xLi 2mnO 3(1-x) Li (Ni 0.7- ymn 0.15co 0.15m y) O 2, can make to be coated through metal oxide, in oxide, metallic element can be one or both mixtures in V, Mn, Mg, Al, covering amount is 1%～6% of lithium-rich manganese-based material molal quantity.
According to preparation method provided by the present invention, step 1: described in anode sizing agent conductive agent be one or more mixtures in conductive black, electrically conductive graphite, acetylene black, carbon nano-tube.Described adhesive is one or more mixtures in PVDF, CMC, PVP, SBR, PAN.Solvent is one or more mixtures in 1-METHYLPYRROLIDONE, N-N-dimethyl pyrrolidone, dimethyl formamide, absolute ethyl alcohol, acetone.
According to preparation method provided by the present invention, the each constituent content described in step 1 in anode sizing agent is: positive electrode 88%～96%, anodal conductive agent 1%～6%, binding agent 1%～6%.The quantity of solvent adding makes the solid content of slurry 40%～60%.
According to preparation method provided by the present invention, step 1: described in silicon be that negative material can for Si-C composite material, silicon nanowires, nano-tube or through the coated nano-tube of carbon, wherein in Si-C composite material, the content of silicon accounts for 4%～20% of total material weight ratio.Described cathode conductive agent is one or more mixtures in graphite, carbon black, acetylene black, carbon fiber, carbon nano-tube.Described negative pole adhesive is one or more mixtures in styrene butadiene rubbers, Kynoar, polyvinyl alcohol, sodium carboxymethylcellulose, acrylonitrile.Solvent is one or both mixtures in water, 1-METHYLPYRROLIDONE or N-N-dimethyl pyrrolidone.
According to preparation method provided by the present invention, step 1: described in each constituent content in cathode size be: silicon is negative material 90%～96%, cathode conductive agent 1%～5%, binding agent 1%～6%.
According to preparation method provided by the present invention, step 2: described in the coated face density of anode sizing agent be 15 × 10 -3g/cm 2～22 × 10 -3g/cm 2, the coated face density of cathode size is 4 × 10 -3g/cm 2～12 × 10 -3g/cm 2.
According to preparation method provided by the present invention, described housing is aluminum hull, box hat or polyalcohol flexible packing.
Wherein, the preparation method of the lithium-rich manganese-based material of described positive pole comprises the steps:
Step 10: according to lithium-rich manganese-based materials chemistry formula xLi 2mnO 3(1-x) Li (Ni 0.7-ymn 0.15co 0.15m y) O 2, component take lithium source, manganese source, nickel source, cobalt source and doped chemical oxide raw material according to stoichiometry and mix in solvent, and raw material is stirred to wet-milling, mixed;
Step 20: transfer to sand mill at the slurry mixing of step 10 and carry out ultra-fine grinding and dispersion, form suspension-turbid liquid;
Step 30: the suspension-turbid liquid in step 20 is carried out to mist projection granulating and obtain lithium-rich manganese-based presoma;
Step 40: the lithium-rich manganese-based presoma of step 30 is carried out obtaining preliminary lithium-rich manganese-based material after low-temperature sintering and high temperature sintering.
Step 50: the preliminary lithium-rich manganese-based material that step 40 sintering is completed joins reactor, and add solvent and hybrid metal element covering in reactor, after stirring in reactor, be transferred to bipyramid dry in except desolventizing, finally powder is finally obtained to element doping and the lithium-rich manganese-based solid solution cathode material of high power capacity through the coated modification of described mixed-metal oxides through double sintering, through the coated first charge-discharge efficiency that can further promote material, increase energy content of battery density.
Wherein, lithium-rich manganese-based anode material xLi in described step 10 2mnO 3(1-x) Li (Ni 0.7-ymn 0.15co 0.15m y) O 2doped chemical M be one or both in Ti, B, wherein 0.01<y<0.05.
Described lithium source in described step 10 is selected from least one in lithium carbonate, lithium hydroxide, lithium acetate or lithium oxalate; Described manganese source is selected from least one in manganese acetate, manganese nitrate, manganese dioxide, mangano-manganic oxide or manganese carbonate; Described nickel is selected from least one in nickel oxalate, nickelous carbonate or nickel nitrate; Described cobalt source is selected from least one in cobalt acetate, cobalt nitrate, cobalt carbonate or cobalt hydroxide.
The stirring wet-milling of described step 10 is that described raw material is added in ball mill, then adds solvent to stir wet-milling 2～4h, and mixing speed is 20～40Hz.
In described step 10 and described step 50, described solvent is selected from one or more the mixture in ethanol, isopropyl alcohol or water, and its addition is for making slurry solid content 20%～25%.
The ultra-fine grinding of described step 20 be in sand mill with under 15～25Hz rotating speed, carry out ultra-fine grinding, disperse 4～6h, grain diameter is reached below 500nm.
Mist projection granulating in described step 30 is the suspension-turbid liquid in step 20 to be squeezed into Centrafugal spray drying tower carry out mist projection granulating; Atomizer speed-frequency in described spray drying tower is more than 250Hz; And the feeding temperature of described Centrafugal spray drying tower is 150～180 ℃, drop temperature is 70～110 ℃.
In described step 40, the sintering of described lithium-rich manganese-based presoma is incubated 2～4 hours when low-temperature sintering at 250～350 ℃, when high temperature sintering, is incubated 8～12 hours at 850～950 ℃.
In described step 50, hybrid metal element covering is that two or more metallic compounds are coated material, and described metallic compound is that slaine or metal oxide are stayed material surface with the form of metal oxide to become two kinds of metal oxides coated after oversintering.Described two kinds of mixed-metal oxides wherein a kind of for helping material to reduce the one in V, the Mn oxide of irreversible capacity first, another for can increase conductivity and stop material and Mg, the Al oxide of electrolyte reaction in one.And the latter's addition is 2%～20% of the former addition molal quantity, total addition is no more than 8% of lithium-rich manganese-based solid-solution material molal quantity.
In described step 50, described double sintering temperature sintering at 400～500 ℃ keeps 3～6h.
Or the preparation method of the lithium-rich manganese-based material of described positive pole comprises the steps:
Step 100: according to lithium-rich manganese-based solid solution cathode material zLi 2mnO 3(1-z) Li (Ni 0.6mn 0.2co 0.2) O 2the component of (0.5≤z≤0.7) is mixed lithium source, manganese source, nickel source, cobalt source raw material by stoichiometric proportion in solvent, and stirs wet-milling acquisition slurry;
Step 200: the described slurry of step 100 through mixing mill evenly after, use sand mill to carry out ultra-fine grinding slurry mixed, and make the grain diameter D in slurry 50below 500nm with form suspension-turbid liquid;
Step 300: obtain lithium-rich manganese-based presoma by carrying out mist projection granulating after the suspension-turbid liquid deironing in step 200;
Step 400: the lithium-rich manganese-based presoma of step 300 is incubated to 2～4h at 250～400 temperature, then obtains preliminary lithium-rich manganese-based material at 850～950 ℃ of insulation 8～14h sintering;
Step 500: the preliminary lithium-rich manganese-based material that step 400 sintering is completed is poured reactor into, add solvent and mixed-metal oxides covering, stir after 1～3h, by slurry be transferred to bipyramid dry in except desolventizing, finally by powder process double sintering, temperature is sintering 3～6h at 400～500 ℃, finally obtains the lithium-rich manganese-based material through the coated modification of mixed-metal oxides.
Wherein, the described lithium source in described step 100 is selected from least one in lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate or lithium fluoride; Described manganese source is selected from least one in manganese acetate, manganese oxalate, manganese sulfate, manganese nitrate, manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide or manganese carbonate; Described nickel source is selected from least one in nickel oxalate, nickel acetate, nickelous carbonate, nickelous sulfate or nickel nitrate; Described cobalt source is selected from least one in cobalt acetate, cobalt oxalate, cobaltous sulfate, cobalt nitrate, cobalt carbonate, cobalt hydroxide or cobalt oxide.
Wherein, the stirring wet-milling of described step 100 is that described raw material is added in ball mill, then adds described solvent to stir wet-milling 2～3 hours, and its mixing speed is 20～30Hz.
Wherein, in described step 100, the solvent that uses is selected from one or more mixtures in ethanol, isopropyl alcohol or water, and its addition is for making slurry solid content 20%～25%.
Wherein, the ultra-fine grinding of described step 200 is to carry out ultra-fine grinding under 15～25Hz rotating speed, to disperse 4～6 hours in sand mill.
Wherein, the mist projection granulating in described step 300 is that the suspension-turbid liquid in step 2 is squeezed in Centrafugal spray drying tower, carries out mist projection granulating; Atomizer frequency in described Centrafugal spray drying tower is 250～300Hz, and the feeding temperature of described Centrafugal spray drying tower is 150～180 ℃, and drop temperature is 70～105 ℃.
Wherein, described mixed-metal oxides covering in described step 500 is mixed-metal oxides, described mixed-metal oxides is selected from two kinds in the oxide of Mg, Ti, V, Mn or Al, and wherein a kind of molal quantity of metal oxide is 5%～20% of another kind of metal oxide molal quantity.
Adopt embodiment to conduct further description the present invention below.
Embodiment 1
Lithium-rich manganese-based anode material is chosen 0.5Li 2mnO 30.5Li (Ni 0.6mn 0.2co 0.2) O 2structure, joins in nmp solvent according to positive electrode 92%, acetylene black 2%, electrically conductive graphite 1%, carbon nano-tube 0.5%, PVDF4.5%, and controlling slurry solid content is 50%.In batch mixer, stir 10 hours under 2500rpm rotating speed, complete the preparation of positive electrode slurry, coating one side surface density is 20 × 10 -3g/cm 2, dual coating, to aluminium foil, after drying, is carried out roll-in to pole piece, and compacted density is 2.9g/cm 3obtain anode pole piece.It is 8% that negative pole adopts the content of Si, and capacity is the Si-C composite material of 550mAh/g left and right, joins in nmp solvent according to Si/C composite material 95%, conductive black 1.5%, CMC1.5%, SBR2%, and controlling slurry solid content is 45%.In batch mixer, stir 8 hours with 2500rpm rotating speed, obtain cathode size, coating one side surface density is 7.6 × 10 -3g/cm 2, dual coating, to Copper Foil, after drying, is carried out roll-in to pole piece, and compacted density is 1.6g/cm 3obtain cathode pole piece.
Positive/negative plate is carried out to anode pole piece and the cathode pole piece to required form of cutting, stackedly be made into required battery core along adopting successively according to anode pole piece, barrier film cathode pole piece, soldering polar ear, and by battery core coating, in battery, inject supporting consumption electrolyte, change into carrying out partial volume after battery seal, be finally assembled into lithium-rich manganese-based flexible-packed battery.
The lithium-rich manganese-based flexible-packed battery of 34.3Ah obtaining under 0.2C current density, charging and discharging curve as threshold voltage 3.67V weight in Fig. 2 be 463g.It is 271.8Wh/kg that measuring and calculating obtains energy content of battery density.
Embodiment 2
Lithium-rich manganese-based anode material is chosen 0.6Li 2mnO 30.4Li (Ni 0.6mn 0.2co 0.2) O 2structure, and this material is through 3%MnO 2and 0.3%Al 2o 3coated.Join in nmp solvent according to positive electrode 93%, acetylene black 1%, conductive black 1%, carbon nano-tube 1%, PVDF4%, controlling slurry solid content is 45%.In batch mixer, stir 12 hours under 2500rpm rotating speed, complete the preparation of positive electrode slurry, coating one side surface density is 19 × 10 -3g/cm 2, dual coating, to aluminium foil, after drying, is carried out roll-in to pole piece, and compacted density is 2.7g/cm 3obtain anode pole piece.It is 10% that negative pole adopts the content of Si, and capacity is the Si-C composite material of 600mAh/g left and right, joins in nmp solvent according to Si/C composite material 96%, conductive black 0.5%, carbon nano-tube 0.5%, CMC1%, SBR2%, and controlling slurry solid content is 45%.In batch mixer, stir 9 hours with 2750rpm rotating speed, obtain cathode size, coating one side surface density is 6.9 × 10 -3g/cm 2, dual coating, to Copper Foil, after drying, is carried out roll-in to pole piece, and compacted density is 1.4g/cm 3obtain cathode pole piece.
Positive/negative plate is carried out to anode pole piece and the cathode pole piece to required form of cutting, stackedly be made into required battery core along adopting successively according to anode pole piece, barrier film cathode pole piece, soldering polar ear, and by battery core coating, in battery, inject supporting consumption electrolyte, change into carrying out partial volume after battery seal, be finally assembled into lithium-rich manganese-based flexible-packed battery.
The lithium-rich manganese-based flexible-packed battery of 35.1Ah obtaining under 0.2C current density, middle threshold voltage 3.66V, battery weight is 458g.Therefore measuring and calculating obtains energy content of battery density and reaches 293.5Wh/kg.
Embodiment 3
Lithium-rich manganese-based anode material is chosen 0.5Li 2mnO 30.5Li (Ni 0.68mn 0.15co 0.15ti 0.02) O 2structure.Join in nmp solvent according to positive electrode 92%, electrically conductive graphite 1.5%, conductive black 0.5%, carbon nano-tube 1.5%, PVDF4.5%, controlling slurry solid content is 48%.In batch mixer, stir 10 hours under 2800rpm rotating speed, complete the preparation of positive electrode slurry, coating one side surface density is 20.5 × 10 -3g/cm 2, dual coating, to aluminium foil, after drying, is carried out roll-in to pole piece, and compacted density is 2.4g/cm 3obtain anode pole piece.It is 12% that negative pole adopts the content of Si, and capacity is the Si-C composite material of 640mAh/g left and right, joins in nmp solvent according to Si/C composite material 95%, conductive black 0.5%, carbon nano-tube 1%, PVP1.5%, SBR2%, and controlling slurry solid content is 40%.In batch mixer, stir 8 hours with 2800rpm rotating speed, obtain cathode size, coating one side surface density is 6.9 × 10 -3g/cm 2, dual coating, to Copper Foil, after drying, is carried out roll-in to pole piece, and compacted density is 1.3g/cm 3obtain cathode pole piece.
Positive/negative plate is carried out to anode pole piece and the cathode pole piece to required form of cutting, stackedly be made into required battery core along adopting successively according to anode pole piece, barrier film cathode pole piece, soldering polar ear, and by battery core coating, in battery, inject supporting consumption electrolyte, change into carrying out partial volume after battery seal, be finally assembled into lithium-rich manganese-based flexible-packed battery.
The lithium-rich manganese-based flexible-packed battery of 36.4Ah obtaining under 0.2C current density, middle threshold voltage 3.62V, battery weight is 424.7g.Therefore measuring and calculating obtains energy content of battery density and reaches 310.3Wh/kg.
Embodiment 4
Lithium-rich manganese-based anode material is chosen 0.5Li 2mnO 30.5Li (Ni 0.68mn 0.15co 0.15ti 0.02) O 2structure, and this material is through 5%MnO 2and 0.5%Al 2o 3coated.According to positive electrode 94%, conductive black 0.5%, carbon nano-tube 1.5%, PVDF4% join in nmp solvent, and controlling slurry solid content is 45%.In batch mixer, stir 11 hours under 3000rpm rotating speed, complete the preparation of positive electrode slurry, coating one side surface density is 19 × 10 -3g/cm 2, dual coating, to aluminium foil, after drying, is carried out roll-in to pole piece, and compacted density is 2.5g/cm 3obtain anode pole piece.Negative pole employing capacity is the silicon nanowire material of 1000mAh/g left and right, is added to the water according to silicon nanowires 94%, conductive black 0.5%, carbon nano-tube 1.5%, PVP2%, SBR2%, and controlling slurry solid content is 38%.In batch mixer, stir 10 hours with 3000rpm rotating speed, obtain cathode size, coating one side surface density is 4.9 × 10 -3g/cm 2, dual coating, to Copper Foil, after drying, is carried out roll-in to pole piece, and compacted density is 1.2g/cm 3obtain cathode pole piece.
Positive/negative plate is carried out to cutting and obtains anode pole piece and the cathode pole piece of required form, stackedly be made into required battery core along adopting successively according to anode pole piece, barrier film cathode pole piece, soldering polar ear, and by battery core coating, in battery, inject supporting consumption electrolyte, change into carrying out partial volume after battery seal, be finally assembled into lithium-rich manganese-based flexible-packed battery.
The lithium-rich manganese-based flexible-packed battery of 35.1Ah obtaining under 0.2C current density, middle threshold voltage 3.55V, battery weight is 384.7g.Therefore measuring and calculating obtains energy content of battery density and reaches 324Wh/kg.
Embodiment 5
Lithium-rich manganese-based anode material is chosen 0.7Li 2mnO 30.3Li (Ni 0.695mn 0.15co 0.15al 0.005) O 2structure, and material is through 5%V 2o 5and 0.5%TiO 2coated, the half-cell 0.2C electric discharge under 4.8V of this material has reached 270mAh/g.According to positive electrode 94%, conductive black 1%, carbon nano-tube 1%, PVDF4% join in nmp solvent, and controlling slurry solid content is 45%.In batch mixer, stir 12 hours under 3000rpm rotating speed, complete the preparation of positive electrode slurry, coating one side surface density is 22 × 10 -3g/cm 2, dual coating, to aluminium foil, after drying, is carried out roll-in to pole piece, and compacted density is 2.4g/cm 3obtain anode pole piece.Negative pole employing capacity is the silicon nanowire material of 1300mAh/g left and right, is added to the water according to silicon nanowires 95%, carbon nano-tube 1%, PVP2%, SBR2%, and controlling slurry solid content is 36%.In batch mixer, stir 10 hours with 3000rpm rotating speed, obtain cathode size, coating one side surface density is 4.5 × 10 -3g/cm 2, dual coating, to Copper Foil, after drying, is carried out roll-in to pole piece, and compacted density is 1.2g/cm 3obtain cathode pole piece.
Positive/negative plate is carried out to cutting and obtains anode pole piece and the cathode pole piece of required form, stackedly be made into required battery core along adopting successively according to anode pole piece, barrier film cathode pole piece, soldering polar ear, and by battery core coating, in battery, inject supporting consumption electrolyte, change into carrying out partial volume after battery seal, be finally assembled into lithium-rich manganese-based flexible-packed battery.
The lithium-rich manganese-based flexible-packed battery of 36.8Ah obtaining under 0.2C current density, middle threshold voltage 3.53V, battery weight is 387g.Therefore measuring and calculating obtains energy content of battery density and reaches 335Wh/kg.
Comparative example 1
Made battery in comparative example 1, choosing equally lithium-rich manganese-based anode material chemical formula is 0.5Li 2mnO 30.5Li (Ni 0.3 3mn 0.33co 0.33) O 2structure, joins in nmp solvent according to positive electrode 92%, acetylene black 2%, electrically conductive graphite 1%, carbon nano-tube 0.5%, PVDF4.5%, and controlling slurry solid content is 50%.In batch mixer, stir 10 hours under 2500rpm rotating speed, complete the preparation of positive electrode slurry, coating one side surface density is 20 × 10 -3g/cm 2, dual coating, to aluminium foil, after drying, is carried out roll-in to pole piece, and compacted density is 2.9g/cm 3obtain anode pole piece.Negative pole adopts traditional native graphite, and 0.1C capacity is 340mAh/g left and right, joins in nmp solvent according to graphite cathode material 95%, conductive black 1.5%, CMC1.5%, SBR2%, and controlling slurry solid content is 45%.In batch mixer, stir 8 hours with 2500rpm rotating speed, obtain cathode size, coating one side surface density is 12.5 × 10 -3g/cm 2, dual coating, to Copper Foil, after drying, is carried out roll-in to pole piece, and compacted density is 1.6g/cm 3obtain cathode pole piece.
Positive/negative plate is carried out to anode pole piece and the cathode pole piece to required form of cutting, stackedly be made into required battery core along adopting successively according to anode pole piece, barrier film cathode pole piece, soldering polar ear, and by battery core coating, in battery, inject supporting consumption electrolyte, change into carrying out partial volume after battery seal, be finally assembled into lithium-rich manganese-based flexible-packed battery.
Under 0.2C current density, test obtains the lithium-rich manganese-based flexible-packed battery of 31.5Ah, and middle threshold voltage 3.69V weight is 461g.It is 252.1Wh/kg that measuring and calculating obtains energy content of battery density.
Battery data in embodiment and comparative example is tested to summary below as shown in table 1:
Table 1:
Adopt as can be seen from Table 1 lithium-rich manganese-based anode material of the present invention and silicium cathode material to match prepared flexible-packed battery and there is very high energy density, along with variation and the silicon of lithium-rich manganese-based mechanism are the lifting of capacity of negative plates, energy density is also progressively strengthened, more than this system can energy content of battery density can reach 300Wh/kg.Relatively in comparative example 1, adopt graphite cathode and the pairing of lithium-rich manganese-based material, energy density only has 252.1Wh/kg, and in the embodiment 1 that adopts same process to make to change Si be that after negative pole, energy density has reached 271.8Wh/kg, changing as seen the energy density of same process battery after battery system can significantly promote.Therefore the target that the electrokinetic cell energy density that " energy-conservation with new-energy automobile estate planning " requires to completing future in the research and development of this direction reaches 300Wh/Kg before the year two thousand twenty will play vital effect.The electrokinetic cell of this system also will more have prospect in future development.
According to the prepared lithium ion battery of this method, in order to obtain the battery of high-energy-density, choose at positive pole the lithium-rich manganese-based material that capacity is higher, in order to make lithium-rich manganese-based material bring into play better performance and to reduce irreversible capacity, the part material of choosing has carried out doping and metal oxide is coated, simultaneously, on negative pole, choosing the silicon that capacity is higher is negative pole, silicon-carbon compound can reach the capacity of 400～800mAh/g, if employing silicon nanowires, more than the capacity that negative pole can provide will reach 1000mAh/g, well beyond the capacity of about 350mAh/g of existing graphite material, this will further significantly promote quality and the volume energy density of material.
Certainly; the present invention also can have other various embodiments; in the situation that not deviating from spirit of the present invention and essence thereof; those of ordinary skill in the art can make according to the present invention various corresponding changes and distortion, but these corresponding changes and distortion all should belong to the protection range of the claims in the present invention.

Claims (12)

1. a lithium battery, is characterized in that, adopts lithium-rich manganese-based material as positive pole, adopts silicon based material as negative pole.
2. lithium battery according to claim 1, is characterized in that, described lithium-rich manganese-based material molecule formula is zLi 2mnO 3(1-z) Li (Ni 0.6mn 0.2co 0.2) O 2, 0.5≤z≤0.7, or xLi 2mnO 3(1-x) Li (Ni 0.7-ymn 0.15co 0.15m y) O 2, 0.4≤x≤0.7, M is doped chemical, 0.01<y<0.05, M is one or both in Ti, B, Al, Mg.
3. lithium battery according to claim 2, is characterized in that, described lithium-rich manganese-based material is selected from 0.5Li 2mnO 30.5Li (Ni 0.6mn 0.2co 0.2) O 2, 0.6Li 2mnO 30.4Li (Ni 0.6mn 0.2co 0.2) O 2, 0.7Li 2mnO 30.3Li (Ni 0.6mn 0.2co 0.2) O 2, 0.4Li 2mnO 30.6Li (Ni 0.65mn 0.15co 0.15ti 0.05) O 2, 0.5Li 2mnO 30.5Li (Ni 0.68mn 0.15co 0.15ti 0.02) O 2, 0.6Li 2mnO 30.4Li (Ni 0.6985mn 0.15co 0.15ti 0.0015) O 2, 0.6Li 2mnO 30.4Li (Ni 0.68mn 0.15co 0.15b 0.02) O 2, 0.7Li 2mnO 30.3Li (Ni 0.697mn 0.15co 0.15al 0.003) O 2or 0.7Li 2mnO 30.3Li (Ni 0.695mn 0.15co 0.15al 0.005) O 2.
4. lithium battery according to claim 1, it is characterized in that, described lithium-rich manganese-based material is coated through metal oxide, in described metal oxide, metallic element is one or both mixtures in V, Mn, Mg or Al, and described metal oxide covering amount is 1%～6% of described lithium-rich manganese-based material molal quantity.
5. lithium battery according to claim 1, it is characterized in that, described silicon is that negative material is Si-C composite material, silicon nanowires, nano-tube or the coated nano-tube of process carbon, and in described Si-C composite material, the content of silicon accounts for 4%～20% of total material weight ratio.
6. a manufacture method for lithium battery, is characterized in that, the lithium-rich manganese-based material of anodal employing is made, and negative pole adopts silicon based material to make.
7. the manufacture method of lithium battery according to claim 6, is characterized in that, comprises the steps:
Step 1: prepare pole piece slurry: the lithium-rich manganese-based material of anodal employing, molecular formula is zLi 2mnO 3(1-z) Li (Ni 0.6mn 0.2co 0.2) O 2, 0.5≤z≤0.7, or xLi 2mnO 3(1-x) Li (Ni 0.7- ymn 0.15co 0. 15m y) O 2, 0.4≤x≤0.7, M is doped chemical, 0.01<y<0.05, M is one or both in Ti, B, Al, Mg, and positive electrode, conductive agent, binding agent, solvent are joined in batch mixer and carry out batch mixing, obtains anode sizing agent; Negative pole adopts silicon based material, and described silicon based material, conductive agent, binding agent and solvent are added in mixing hollander and carry out batch mixing, obtains cathode size;
Step 2: positive and negative electrode pole piece preparation: anode sizing agent is coated on plus plate current-collecting body, with 110 ℃～150 degrees Celsius dry oven dry, then carries out roller compaction in baking oven, compacted density is controlled at 2.4～3.1g/cm 3, obtain anode pole piece; Cathode size is coated on negative current collector, in baking oven, dries with 90～110 ℃, carry out pair roller roll extrusion, compacted density is at 1.2～1.7g/cm 3, obtain cathode pole piece;
Step 3: assembled battery: adopt stacked or takeup type to be assembled into battery core according to positive plate, barrier film and negative plate successively order pole piece, the anode pole piece lug of battery core and cathode pole piece lug are welded together respectively, and battery core is packed in battery container;
Step 4: fluid injection, change into: inject the electrolyte in battery, and sealing, the battery assembling is carried out to partial volume and change into and obtain final battery.
8. the manufacture method of lithium battery according to claim 7, is characterized in that, described in described step 1, lithium-rich manganese-based material is selected from 0.5Li 2mnO 30.5Li (Ni 0.6mn 0.2co 0.2) O 2, 0.6Li 2mnO 30.4Li (Ni 0.6mn 0.2co 0.2) O 2, 0.7Li 2mnO 30.3Li (Ni 0.6mn 0.2co 0.2) O 2, 0.4Li 2mnO 30.6Li (Ni 0.65mn 0.15co 0.15ti 0.05) O 2, 0.5Li 2mnO 30.5Li (Ni 0.68mn 0.15co 0.15ti 0.02) O 2, 0.6Li 2mnO 30.4Li (Ni 0.6985mn 0.15co 0.15ti 0.0015) O 2, 0.6Li 2mnO 30.4Li (Ni 0.68mn 0.15co 0.15b 0.02) O 2, 0.7Li 2mnO 30.3Li (Ni 0.697mn 0.15co 0.15al 0.003) O 2or 0.7Li 2mnO 30.3Li (Ni 0.695mn 0.15co 0.15al 0. 005) O 2.
9. the manufacture method of lithium battery according to claim 7, is characterized in that, lithium-rich manganese-based material zLi described in described step 1 2mnO 3(1-z) Li (Ni 0.6mn 0.2co 0.2) O 2or xLi 2mnO 3(1-x) Li (Ni 0.7- ymn 0.15co 0.15m y) O 2coated through metal oxide, in described metal oxide, metallic element is one or both mixtures in V, Mn, Mg, Al, and the covering amount of described metal oxide is 1%～6% of lithium-rich manganese-based material molal quantity.
10. the manufacture method of lithium battery according to claim 7, is characterized in that, in described step 1, conductive agent described in described anode sizing agent is one or more mixtures in conductive black, electrically conductive graphite, acetylene black, carbon nano-tube; Described adhesive is one or more mixtures in PVDF, CMC, PVP, SBR, PAN; Described solvent is one or more mixtures in 1-METHYLPYRROLIDONE, N-N-dimethyl pyrrolidone, dimethyl formamide, absolute ethyl alcohol, acetone; Each constituent content in described anode sizing agent is: described positive electrode 88%～96%, and described conductive agent 1%～6%, described binding agent 1%～6%, the amount of the described solvent adding is to make the solid content of slurry 40%～60%.
The manufacture method of 11. lithium batteries according to claim 7, it is characterized in that, silicon based material described in described step 1 is Si-C composite material, silicon nanowires, nano-tube or the coated nano-tube of process carbon, and wherein in Si-C composite material, the content of silicon accounts for 4%～20% of total material weight ratio; Conductive agent described in described cathode size is one or more mixtures in graphite, carbon black, acetylene black, carbon fiber, carbon nano-tube; Described adhesive is one or more mixtures in styrene butadiene rubbers, Kynoar, polyvinyl alcohol, sodium carboxymethylcellulose, acrylonitrile, and described solvent is one or both mixtures in water, 1-METHYLPYRROLIDONE or N-N-dimethyl pyrrolidone; Each constituent content in described cathode size is: described silicon based material 90%～96%, and described conductive agent 1%～5%, described binding agent 1%～6%, the amount of the described solvent adding makes the solid content of slurry 35%～50%.
The manufacture method of 12. lithium batteries according to claim 7, is characterized in that, the coated face density of anode sizing agent described in described step 2 is 15 × 10 -3g/cm 2～22 × 10 -3g/cm 2, the coated face density of described cathode size is 4 × 10 -3g/cm 2～12 × 10 -3g/cm 2.
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CN108539258A (en) * 2018-05-08 2018-09-14 中国电力科学研究院有限公司 A kind of trapezoidal ion battery and preparation method thereof
CN109148893A (en) * 2018-08-27 2019-01-04 江苏中兴派能电池有限公司 One kind being based on lithium ion battery negative material SiOx/C combination electrode and preparation method
CN111313008A (en) * 2020-03-05 2020-06-19 厦门大学 Magnesium-containing lithium-rich manganese-based positive electrode and preparation method thereof
CN111600013A (en) * 2020-05-12 2020-08-28 武汉工程大学 Manganese source precursor, manganese-based lithium battery positive electrode material and preparation method thereof
CN113594405A (en) * 2020-04-30 2021-11-02 通用汽车环球科技运作有限责任公司 Solvent-free dry powder process for incorporating ceramic particles into electrochemical cell components
CN114583385A (en) * 2022-03-02 2022-06-03 上海兰钧新能源科技有限公司 Lithium battery composite safety diaphragm, lithium battery cell and corresponding preparation method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1962364A1 (en) * 2007-02-26 2008-08-27 Samsung SDI Co., Ltd. Rechargeable lithium battery
CN103560250A (en) * 2013-11-07 2014-02-05 天津市捷威动力工业有限公司 Lithium ion battery adopting lithium-rich manganese-based material as positive electrode and preparation method of lithium ion battery
CN103606704A (en) * 2013-11-15 2014-02-26 江苏天鹏电源有限公司 High-energy density lithium ion battery

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1962364A1 (en) * 2007-02-26 2008-08-27 Samsung SDI Co., Ltd. Rechargeable lithium battery
CN103560250A (en) * 2013-11-07 2014-02-05 天津市捷威动力工业有限公司 Lithium ion battery adopting lithium-rich manganese-based material as positive electrode and preparation method of lithium ion battery
CN103606704A (en) * 2013-11-15 2014-02-26 江苏天鹏电源有限公司 High-energy density lithium ion battery

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CN105932274A (en) * 2016-07-06 2016-09-07 福建师范大学 Preparation method of titanium-dioxide-coated spinel lithium-rich lithium manganite positive electrode material
CN105932262A (en) * 2016-07-06 2016-09-07 福建师范大学 Preparation method of spinel-coated lithium-rich lithium manganate anode material
CN106252572A (en) * 2016-09-09 2016-12-21 贵州梅岭电源有限公司 A kind of energy-density lithium ion battery and preparation method thereof
CN106784843A (en) * 2016-12-28 2017-05-31 中天储能科技有限公司 It is a kind of more than 300wh/kg high-energy-densities, the preparation method of high security battery
CN107369817A (en) * 2017-06-22 2017-11-21 华南理工大学 A kind of rich lithium polynary anode material for lithium-ion batteries of carbon coating and preparation method thereof
CN108183242A (en) * 2017-11-20 2018-06-19 南京航空航天大学 A kind of preparation method of novel lithium-air battery and its anode
CN108183242B (en) * 2017-11-20 2021-01-08 南京航空航天大学 Lithium-air battery and preparation method of positive electrode thereof
CN108539258A (en) * 2018-05-08 2018-09-14 中国电力科学研究院有限公司 A kind of trapezoidal ion battery and preparation method thereof
CN109148893A (en) * 2018-08-27 2019-01-04 江苏中兴派能电池有限公司 One kind being based on lithium ion battery negative material SiOx/C combination electrode and preparation method
CN111313008A (en) * 2020-03-05 2020-06-19 厦门大学 Magnesium-containing lithium-rich manganese-based positive electrode and preparation method thereof
CN111313008B (en) * 2020-03-05 2021-07-16 厦门大学 Magnesium-containing lithium-rich manganese-based positive electrode and preparation method thereof
CN113594405A (en) * 2020-04-30 2021-11-02 通用汽车环球科技运作有限责任公司 Solvent-free dry powder process for incorporating ceramic particles into electrochemical cell components
CN111600013A (en) * 2020-05-12 2020-08-28 武汉工程大学 Manganese source precursor, manganese-based lithium battery positive electrode material and preparation method thereof
CN114583385A (en) * 2022-03-02 2022-06-03 上海兰钧新能源科技有限公司 Lithium battery composite safety diaphragm, lithium battery cell and corresponding preparation method
CN114583385B (en) * 2022-03-02 2024-03-15 上海兰钧新能源科技有限公司 Lithium battery composite safety diaphragm, lithium battery cell and corresponding preparation method

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