CN106997965B - A kind of preparation method of lithium ion battery - Google Patents

A kind of preparation method of lithium ion battery Download PDF

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CN106997965B
CN106997965B CN201710253463.2A CN201710253463A CN106997965B CN 106997965 B CN106997965 B CN 106997965B CN 201710253463 A CN201710253463 A CN 201710253463A CN 106997965 B CN106997965 B CN 106997965B
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lithium ion
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nickel foam
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CN106997965A (en
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章明耀
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Anhui Liyuan new energy Co., Ltd.
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M10/058—Construction or manufacture
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    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • 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
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • H—ELECTRICITY
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    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H01M4/808—Foamed, spongy materials
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    • Y02E60/10—Energy storage using batteries
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Abstract

The invention discloses a kind of preparation method of lithium ion battery, detailed processes are as follows: prepares carbon-coated iron phosphate lithium positive pole piece using nickel foam as matrix using the method for co-precipitation first；Then using nickel foam as substrate, Co is grown3O4Nano-wire array, and using the method for constant pressure electro-deposition in Co3O4Nano-wire array surface deposited silicon layer, and carbon-coating is sprayed in silicon surface, negative electrode tab is made, is finally sequentially overlapped positive plate, diaphragm, negative electrode tab, the volume heart is made, it is sealed in battery case, injects electrolyte, preliminary filling, aging, chemical conversion, it is high that lithium ion battery energy density made from lithium ion battery this method is made, power is big, good cycle, and preparation cost is low.

Description

A kind of preparation method of lithium ion battery
Technical field
The present invention relates to the preparation fields of battery, are specifically related to a kind of preparation method of lithium ion battery.
Background technique
Under world's energy shortages and the macroscopic of environmental pollution, many countries will develop new in the 21st century, Important component of the type energy (wind energy, water energy, ocean energy and solar energy etc.) as energy strategy, and propose specific New energy developing goal, but the application of new energy is constrained using lithium battery as the electric energy storage technology represented, therefore, preparation The lithium ion battery of large capacity, low cost, long-life and safety is the emphasis of current lithium ion battery industry development.
Lithium battery relies primarily on Li+Insertion between positive and negative anodes active material and deintercalation carry out work, when charging, Li+From Deintercalation in positive-active compound is embedded in cathode lattice by electrolyte and diaphragm, and rich lithium state is presented in cathode, while in order to tie up The balance of charge is held, the electronics of equal quantities is migrated by anode to cathode through external circuit；When electric discharge, Li+From negative electrode active material Deintercalation, by electrolyte and diaphragm, insertion anode, while the electronics of equal quantities is migrated by cathode to anode through external circuit, this Li+Insertion and deintercalation process between positive and negative anodes active material produce electric current, realize the charge and discharge electric work of lithium ion battery Energy.Due to Li+There is relatively fixed position and space, therefore the reversibility of lithium ion battery in positive and negative anodes active material Well, and in charge and discharge process lithium metal is not present, eliminates the formation condition of Li dendrite, ensure that the circulation of lithium battery Performance and security performance.
Certainly, lithium ion battery is there is also some disadvantages, and such as fast charge-discharge performance is poor, heavy-current discharge performance not Dali Think, the problems such as internal driving is higher.The performance of lithium ion battery material determines the performance of lithium ion battery to varying degrees Whether good.It wherein influences maximum to be positive and negative pole material, they are the key factors for improving performance of lithium ion battery.Therefore it wants The lithium ion secondary battery haveing excellent performance is made, first has to prepare the excellent lithium ion battery plus-negative plate material of electric property.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of lithium ion battery, lithium ion battery made from this method is first Charge/discharge capacity is big, good cycling stability, excellent combination property.
To achieve the above object, the invention adopts the following technical scheme:
A kind of preparation method of lithium ion battery, comprising the following steps:
(1) by nickel foam after low-kappa number be used as conductive current collector, by source of iron, phosphorus source, glucose be dissolved in water be made it is mixed Solution A is closed, Quadrafos is added, is uniformly mixed obtained mixed solution B, precipitating reagent is dissolved in water, precipitant solution is made, will steeped Foam nickel is added in reactor, and then while respectively mixed solution B, precipitant solution are added in reactor, and co-precipitation is anti- 3-7h is answered, obtains iron phosphorus presoma after obtained product washing is dry；
(2) by iron phosphorus presoma obtained above and lithium hydroxide mixed grinding uniformly after high temperature sintering tabletting, be sliced To LiFePO4Positive plate；
(3) nickel foam is used as to conductive current collector after low-kappa number；Cobalt nitrate, urea and ammonium fluoride and water are mixed equal Mixed liquor, is then transferred in reaction kettle by even obtained mixed liquor, and the nickel foam of acid processing obtained above is added；Heating is anti- It answers, is cooled to room temperature after the reaction was completed, obtained solid product washing is dry, Co is made in high-temperature calcination3O4Nano-wire array；
(4) soluble silicon source is dissolved in ionic liquid, inertia electrolyte is made, then with Co obtained above3O4Nanometer Linear array is classified as cathode, and inert electrode carries out constant pressure electro-deposition as anode, electro-deposition product by organic matter cleaning, remove from Sub- liquid obtains the Co for having silicon layer to surface3O4Nano wire finally carries out surface spray C processing, and dry, negative electrode tab is made in tabletting；
(5) positive plate, diaphragm, negative electrode tab are sequentially overlapped, the volume heart are made, is sealed in battery case, inject electrolyte, Lithium ion battery is made in preliminary filling, aging, chemical conversion.
As a preferred embodiment of the above technical solution, in step (1), the additional amount of the Quadrafos is phosphorus source, source of iron and Portugal The 5-10% of grape sugar total weight.
As a preferred embodiment of the above technical solution, the concrete operations of low-kappa number nickel foam are as follows: the nitre by nickel foam 30% 5min is impregnated in aqueous acid.
As a preferred embodiment of the above technical solution, in step (1), the adding speed of mixed solution B and precipitant solution is distinguished Are as follows: 1-5 ls/h, 0.8-2.6 ls/h.
As a preferred embodiment of the above technical solution, in step (3), the preparation method of the mixed liquor specifically: by 1-3g nitre Sour cobalt, 0.3-0.5g ammonium fluoride and 1-3g urea are dissolved in 50mL distilled water, are slowly stirred 30min.
As a preferred embodiment of the above technical solution, in step (3), the temperature of the heating reaction is 110-130 DEG C, reaction Time is 1-5h.
As a preferred embodiment of the above technical solution, in step (3), the condition of the high-temperature calcination are as follows: calcined at 350-450 DEG C 1-4h。
As a preferred embodiment of the above technical solution, in step (4), the condition of the constant pressure electro-deposition are as follows: with the direct of preparation Grow the Co of nickel foam3O4For nano-wire array as cathode, Pt net electrode contains 0.25M as inert anode, at 50 DEG C SiCl4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage be -2.4V, time 1-5h.
As a preferred embodiment of the above technical solution, in step (5), the diaphragm be by nano aluminium oxide and micrometer alumina with And pore creating material mixing, secondary high-temperature are sintered multiaperture pellumina obtained, and with a thickness of 80-120 μm, pore size 100- 300nm。
As a preferred embodiment of the above technical solution, in step (2), the temperature of the high temperature sintering is 720-960 DEG C, and the time is 30-120min。
LiFePO4Exist in the form of fosfosiderite in nature, belong to olivine-type structure, is rhombic system, space group For Pnmb.Wherein O atom arranges in such a way that six sides being slightly mispositioned are tightly packed, in Li and Fe atom filling octahedral interstices, Form FeO6And LiO6Octahedron, P occupy tetrahedron gap, form PO4Tetrahedron.One FeO6Octahedra and two eight LiO6 Face body and a PO4Tetrahedron is connected with total side；One PO4Tetrahedron also with deformation octahedron FeO6And LiO6Side altogether.In FeO6 Layer ask, adjacent LiO6Two O atoms on the shared rib of octahedron, are connected and form three-layer laminated structure, be conducive to Li+In Abjection and insertion in charge and discharge process.And LiFePO4It is converted into FePO4Volume only reduces 6.81%, and negative electrode material is being filled Volume can become larger in discharge process, and the total volume for allowing for entire inside battery in this way varies less, therefore the positive electrode has There is good cycle performance.But due to the FeO of corner-sharing in olivine structural6Octahedral presence, it is low to reduce its conductivity, thus Lead to LiFePO4Electric conductivity and high rate performance it is poor.The present invention, as substrate, is directly prepared using nickel foam on its surface Positive electrode, and carry out carbon and be modified, cost, and the electric conductivity of positive electrode have been saved in the addition for eliminating conductive agent and binder It can be effectively improved.
Co3O4Irreversible capacity is larger for the first time when negative electrode material of the nano wire as lithium ion battery, and the rate of decay is very fast, The present invention grows Co by substrate of nickel foam first3O4Nano-wire array, then using ionic liquid as electrolyte, in Co3O4Nanometer Constant pressure electro-deposition one layer of silicon layer in linear array surface finally sprays C processing, and negative electrode material electric conductivity obtained is high, and specific capacity is big, circulation Stability is good.
Compared with prior art, the invention has the following advantages that
The present invention prepares positive electrode using the method for co-precipitation, and before coprecipitation reaction, the present invention is in reactant Mixed liquor in Quadrafos is added, can with iron, phosphorus formed complex compound, effectively control its precipitating speed so that system The positive electrode tap density obtained is big, and the complex compound that Quadrafos and iron, phosphorus are formed is more stable, will not change the acid of solution Alkalinity, the cladding of carbon layer on surface effectively increase the electric conductivity of positive electrode, and using nickel foam as base when present invention co-precipitation Bottom, large specific surface area, the addition that can be improved the quality of active material, and eliminate binder and conductive black etc. are saved Cost；
When preparing cell negative electrode material, the present invention grows Co first using nickel foam as substrate, on its surface3O4Nano wire Array, then using ionic liquid as electrolyte, in its one layer of silicon layer of surface constant pressure electro-deposition, relative to original sol-gal process Silicon layer is prepared, this method avoid a large amount of volatilization problems using with solvent of organic solvent, safer environmental protection, silicon layers obtained For unformed silicon, surface is easy to generate layer of silicon dioxide, the volume change of Si in charge and discharge process is effectively inhibited, so that should Negative electrode material chemical property is more preferable.
Specific embodiment:
In order to better understand the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solving The present invention is released, any restriction will not be constituted to the present invention.
Embodiment 1
A kind of preparation method of lithium ion battery, comprising the following steps:
(1) nickel foam is impregnated in 30% aqueous solution of nitric acid after 5min as conductive current collector, by source of iron, phosphorus source, Glucose is dissolved in water and mixed solution A is made, and Quadrafos is added, and is uniformly mixed obtained mixed solution B, precipitating reagent is dissolved in water system Precipitant solution is obtained, nickel foam is added in reactor, then while is respectively added to mixed solution B, precipitant solution In reactor, coprecipitation reaction 3-7h obtains iron phosphorus presoma after obtained product washing is dry；Wherein, Quadrafos plus Enter 5% that amount is phosphorus source, source of iron and glucose total weight；The adding speed of mixed solution B and precipitant solution be respectively as follows: 1 liter/ Hour, 0.8 l/h；
(2) by iron phosphorus presoma obtained above and lithium hydroxide mixed grinding it is uniform after, be sintered at 720 DEG C 100min, tabletting, slice obtain LiFePO4Positive plate；
(3) conductive current collector is used as after nickel foam to be impregnated to 5min in 30% aqueous solution of nitric acid；By 1g cobalt nitrate, 0.5g ammonium fluoride and 1g urea are dissolved in 50mL distilled water, are slowly stirred 30min and mixed liquor is made, then shift mixed liquor To reaction kettle, and the nickel foam of acid processing obtained above is added；5h is reacted at 110 DEG C, is cooled to room after the reaction was completed Temperature, obtained solid product washing is dried, Co is made in calcining 4h at 350 DEG C3O4Nano-wire array；
(4) soluble silicon source is dissolved in ionic liquid, inertia electrolyte is made, then with Co obtained above3O4Nanometer Linear array is classified as cathode, and inert electrode carries out constant pressure electro-deposition as anode, electro-deposition product by organic matter cleaning, remove from Sub- liquid obtains the Co for having silicon layer to surface3O4Nano wire finally carries out surface spray C processing, and dry, negative electrode tab is made in tabletting；Its In, the condition of constant pressure electro-deposition are as follows: with the Co of the direct growth nickel foam of preparation3O4Nano-wire array is as cathode, Pt net electrode As inert anode, contain 0.25MSiCl at 50 DEG C4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage be -2.4V, Time is 1h；
(5) positive plate, diaphragm, negative electrode tab are sequentially overlapped, the volume heart are made, is sealed in battery case, inject electrolyte, Lithium ion battery is made in preliminary filling, aging, chemical conversion.
Wherein, diaphragm is mixed by nano aluminium oxide and micrometer alumina and pore creating material, made from secondary high-temperature sintering Multiaperture pellumina, with a thickness of 80 μm, pore size 100nm.
Embodiment 2
A kind of preparation method of lithium ion battery, comprising the following steps:
(1) nickel foam is impregnated in 30% aqueous solution of nitric acid after 5min as conductive current collector, by source of iron, phosphorus source, Glucose is dissolved in water and mixed solution A is made, and Quadrafos is added, and is uniformly mixed obtained mixed solution B, precipitating reagent is dissolved in water system Precipitant solution is obtained, nickel foam is added in reactor, then while is respectively added to mixed solution B, precipitant solution In reactor, coprecipitation reaction 3-7h obtains iron phosphorus presoma after obtained product washing is dry；Wherein, Quadrafos plus Enter 10% that amount is phosphorus source, source of iron and glucose total weight；The adding speed of mixed solution B and precipitant solution is respectively as follows: 5 L/h, 2.6 ls/h；
(2) by iron phosphorus presoma obtained above and lithium hydroxide mixed grinding it is uniform after, be sintered 30min at 960 DEG C, Tabletting, slice obtain LiFePO4Positive plate；
(3) conductive current collector is used as after nickel foam to be impregnated to 5min in 30% aqueous solution of nitric acid；By 3g cobalt nitrate, 0.3g ammonium fluoride and 3g urea are dissolved in 50mL distilled water, are slowly stirred 30min and mixed liquor is made, then shift mixed liquor To reaction kettle, and the nickel foam of acid processing obtained above is added；1h is reacted at 130 DEG C, is cooled to room after the reaction was completed Temperature, obtained solid product washing is dried, Co is made in calcining 1h at 450 DEG C3O4Nano-wire array；
(4) soluble silicon source is dissolved in ionic liquid, inertia electrolyte is made, then with Co obtained above3O4Nanometer Linear array is classified as cathode, and inert electrode carries out constant pressure electro-deposition as anode, electro-deposition product by organic matter cleaning, remove from Sub- liquid obtains the Co for having silicon layer to surface3O4Nano wire finally carries out surface spray C processing, and dry, negative electrode tab is made in tabletting；Its In, the condition of constant pressure electro-deposition are as follows: with the Co of the direct growth nickel foam of preparation3O4Nano-wire array is as cathode, Pt net electrode As inert anode, contain 0.25MSiCl at 50 DEG C4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage be -2.4V, Time is 5h；
(5) positive plate, diaphragm, negative electrode tab are sequentially overlapped, the volume heart are made, is sealed in battery case, inject electrolyte, Lithium ion battery is made in preliminary filling, aging, chemical conversion.
Wherein, diaphragm is mixed by nano aluminium oxide and micrometer alumina and pore creating material, made from secondary high-temperature sintering Multiaperture pellumina, with a thickness of 120 μm, pore size 100nm.
Embodiment 3
A kind of preparation method of lithium ion battery, comprising the following steps:
(1) nickel foam is impregnated in 30% aqueous solution of nitric acid after 5min as conductive current collector, by source of iron, phosphorus source, Glucose is dissolved in water and mixed solution A is made, and Quadrafos is added, and is uniformly mixed obtained mixed solution B, precipitating reagent is dissolved in water system Precipitant solution is obtained, nickel foam is added in reactor, then while is respectively added to mixed solution B, precipitant solution In reactor, coprecipitation reaction 3-7h obtains iron phosphorus presoma after obtained product washing is dry；Wherein, Quadrafos plus Enter 7% that amount is phosphorus source, source of iron and glucose total weight；The adding speed of mixed solution B and precipitant solution be respectively as follows: 2 liters/ Hour, 1.2 ls/h；
(2) by iron phosphorus presoma obtained above and lithium hydroxide mixed grinding it is uniform after, be sintered at 750 DEG C 120min, tabletting, slice obtain LiFePO4Positive plate；
(3) conductive current collector is used as after nickel foam to be impregnated to 5min in 30% aqueous solution of nitric acid；By 1.5g cobalt nitrate, 0.45g ammonium fluoride and 1.5g urea are dissolved in 50mL distilled water, are slowly stirred 30min and mixed liquor is made, then by mixed liquor It is transferred in reaction kettle, and the nickel foam of acid processing obtained above is added；2h is reacted at 110 DEG C, is cooled down after the reaction was completed To room temperature, obtained solid product washing is dried, Co is made in calcining 3h at 400 DEG C3O4Nano-wire array；
(4) soluble silicon source is dissolved in ionic liquid, inertia electrolyte is made, then with Co obtained above3O4Nanometer Linear array is classified as cathode, and inert electrode carries out constant pressure electro-deposition as anode, electro-deposition product by organic matter cleaning, remove from Sub- liquid obtains the Co for having silicon layer to surface3O4Nano wire finally carries out surface spray C processing, and dry, negative electrode tab is made in tabletting；Its In, the condition of constant pressure electro-deposition are as follows: with the Co of the direct growth nickel foam of preparation3O4Nano-wire array is as cathode, Pt net electrode As inert anode, contain 0.25MSiCl at 50 DEG C4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage be -2.4V, Time is 2h；
(5) positive plate, diaphragm, negative electrode tab are sequentially overlapped, the volume heart are made, is sealed in battery case, inject electrolyte, Lithium ion battery is made in preliminary filling, aging, chemical conversion.
Wherein, diaphragm is mixed by nano aluminium oxide and micrometer alumina and pore creating material, made from secondary high-temperature sintering Multiaperture pellumina, with a thickness of 90 μm, pore size 200nm.
Embodiment 4
A kind of preparation method of lithium ion battery, comprising the following steps:
(1) nickel foam is impregnated in 30% aqueous solution of nitric acid after 5min as conductive current collector, by source of iron, phosphorus source, Glucose is dissolved in water and mixed solution A is made, and Quadrafos is added, and is uniformly mixed obtained mixed solution B, precipitating reagent is dissolved in water system Precipitant solution is obtained, nickel foam is added in reactor, then while is respectively added to mixed solution B, precipitant solution In reactor, coprecipitation reaction 3-7h obtains iron phosphorus presoma after obtained product washing is dry；Wherein, Quadrafos plus Enter 7% that amount is phosphorus source, source of iron and glucose total weight；The adding speed of mixed solution B and precipitant solution be respectively as follows: 3 liters/ Hour, 1.5 ls/h；
(2) by iron phosphorus presoma obtained above and lithium hydroxide mixed grinding it is uniform after, be sintered at 850 DEG C 100min, tabletting, slice obtain LiFePO4Positive plate；
(3) conductive current collector is used as after nickel foam to be impregnated to 5min in 30% aqueous solution of nitric acid；By 2g cobalt nitrate, 0.4g ammonium fluoride and 2g urea are dissolved in 50mL distilled water, are slowly stirred 30min and mixed liquor is made, then shift mixed liquor To reaction kettle, and the nickel foam of acid processing obtained above is added；3h is reacted at 120 DEG C, is cooled to room after the reaction was completed Temperature, obtained solid product washing is dried, Co is made in calcining 3h at 400 DEG C3O4Nano-wire array；
(4) soluble silicon source is dissolved in ionic liquid, inertia electrolyte is made, then with Co obtained above3O4Nanometer Linear array is classified as cathode, and inert electrode carries out constant pressure electro-deposition as anode, electro-deposition product by organic matter cleaning, remove from Sub- liquid obtains the Co for having silicon layer to surface3O4Nano wire finally carries out surface spray C processing, and dry, negative electrode tab is made in tabletting；Its In, the condition of constant pressure electro-deposition are as follows: with the Co of the direct growth nickel foam of preparation3O4Nano-wire array is as cathode, Pt net electrode As inert anode, contain 0.25MSiCl at 50 DEG C4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage be -2.4V, Time is 4h；
(5) positive plate, diaphragm, negative electrode tab are sequentially overlapped, the volume heart are made, is sealed in battery case, inject electrolyte, Lithium ion battery is made in preliminary filling, aging, chemical conversion.
Wherein, diaphragm is mixed by nano aluminium oxide and micrometer alumina and pore creating material, made from secondary high-temperature sintering Multiaperture pellumina, with a thickness of 100 μm, pore size 200nm.
Embodiment 5
A kind of preparation method of lithium ion battery, comprising the following steps:
(1) nickel foam is impregnated in 30% aqueous solution of nitric acid after 5min as conductive current collector, by source of iron, phosphorus source, Glucose is dissolved in water and mixed solution A is made, and Quadrafos is added, and is uniformly mixed obtained mixed solution B, precipitating reagent is dissolved in water system Precipitant solution is obtained, nickel foam is added in reactor, then while is respectively added to mixed solution B, precipitant solution In reactor, coprecipitation reaction 3-7h obtains iron phosphorus presoma after obtained product washing is dry；Wherein, Quadrafos plus Enter 8% that amount is phosphorus source, source of iron and glucose total weight；The adding speed of mixed solution B and precipitant solution is respectively as follows: 4.5 L/h, 2 ls/h；
(2) by iron phosphorus presoma obtained above and lithium hydroxide mixed grinding it is uniform after, be sintered 50min at 900 DEG C, Tabletting, slice obtain LiFePO4Positive plate；
(3) conductive current collector is used as after nickel foam to be impregnated to 5min in 30% aqueous solution of nitric acid；By 2.5g cobalt nitrate, 0.35g ammonium fluoride and 2.5g urea are dissolved in 50mL distilled water, are slowly stirred 30min and mixed liquor is made, then by mixed liquor It is transferred in reaction kettle, and the nickel foam of acid processing obtained above is added；4.5h is reacted at 120 DEG C, it is cold after the reaction was completed But to room temperature, obtained solid product washing is dried, Co is made in calcining 3h at 400 DEG C3O4Nano-wire array；
(4) soluble silicon source is dissolved in ionic liquid, inertia electrolyte is made, then with Co obtained above3O4Nanometer Linear array is classified as cathode, and inert electrode carries out constant pressure electro-deposition as anode, electro-deposition product by organic matter cleaning, remove from Sub- liquid obtains the Co for having silicon layer to surface3O4Nano wire finally carries out surface spray C processing, and dry, negative electrode tab is made in tabletting；Its In, the condition of constant pressure electro-deposition are as follows: with the Co of the direct growth nickel foam of preparation3O4Nano-wire array is as cathode, Pt net electrode As inert anode, contain 0.25MSiCl at 50 DEG C4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage be -2.4V, Time is 4h；
(5) positive plate, diaphragm, negative electrode tab are sequentially overlapped, the volume heart are made, is sealed in battery case, inject electrolyte, Lithium ion battery is made in preliminary filling, aging, chemical conversion.
Wherein, diaphragm is mixed by nano aluminium oxide and micrometer alumina and pore creating material, made from secondary high-temperature sintering Multiaperture pellumina, with a thickness of 110 μm, pore size 200nm.
Comparative example 1
Quadrafos is added without in the preparation process of positive electrode, other conditions and embodiment 5 are identical.
Comparative example 2
Citric acid is added in the preparation process of positive electrode and substitutes Quadrafos, other conditions and embodiment 5 are identical.
Comparative example 3
Negative electrode material is Co3O4Nano-wire array, surface do not have silicon layer and carbon-coating, and other conditions and embodiment 5 are identical.
Lithium ion battery produced by the present invention is tested for the property below.
Electrochemical property test:
Room temperature charge and discharge are carried out to above-mentioned battery with the electric current of 0.5C, recycles 500 times, tests the cyclicity of lithium ion battery It can, the specific steps are as follows: (1) constant-current discharge: electric current 0.5C, blanking voltage 3V；(2) it shelves: 5 minutes；(3) constant current constant voltage Charging: 0.5C constant-current charge to voltage 4.2V, then 4.2V constant-voltage charge, cut-off current 0.05C；(4) it shelves: 5 minutes； (5) constant-current discharge: electric current 0.5C, blanking voltage 3V；(6) it shelves: 5 minutes；(7) it cycle-index: 500 times, is opened from (3) Begin；(8) terminate.For safety, it is 4.5V that charging upper limit, which is usually arranged, and charging lower limit is 2.5V.
After tested, the first discharge specific capacity of lithium ion battery made from embodiment 1 to embodiment 5 is 203.5- 212.3mAh/g, after recycling 500 times, specific discharge capacity conservation rate is 98.9% or more.
The first discharge specific capacity of the lithium ion battery of comparative example 1 is 137.5mAh/g, and after recycling 500 times, discharge specific volume Measuring conservation rate is 73.5%.
The first discharge specific capacity of the lithium ion battery of comparative example 2 is 185.9mAh/g, and after recycling 500 times, discharge specific volume Measuring conservation rate is 81.9%.
The discharge capacity for the first time of the lithium ion battery of comparative example 3 is 109.5mAh/g, after recycling 500 times, specific discharge capacity Conservation rate is 60.5%.

Claims (10)

1. a kind of preparation method of lithium ion battery, which comprises the following steps:
(1) by nickel foam after low-kappa number be used as conductive current collector, by source of iron, phosphorus source, glucose be dissolved in water be made mixing it is molten Quadrafos is added in liquid A, is uniformly mixed obtained mixed solution B, precipitating reagent is dissolved in water, precipitant solution is made, by nickel foam It is added in reactor, then while respectively mixed solution B, precipitant solution is added in reactor, coprecipitation reaction 3- 7h obtains iron phosphorus presoma after obtained product washing is dry；
(2) by iron phosphorus presoma obtained above and lithium hydroxide mixed grinding, uniformly rear high temperature sintering tabletting, slice are obtained LiFePO4Positive plate；
(3) nickel foam is used as to conductive current collector after low-kappa number；Cobalt nitrate, urea and ammonium fluoride and water are uniformly mixed system Mixed liquor is obtained, then mixed liquor is transferred in reaction kettle, and the nickel foam of acid processing obtained above is added；Heating reaction, It is cooled to room temperature after the reaction was completed, obtained solid product washing is dry, Co is made in high-temperature calcination3O4Nano-wire array；
(4) soluble silicon source is dissolved in ionic liquid, inertia electrolyte is made, then with Co obtained above3O4Nanometer linear array It is classified as cathode, inert electrode carries out constant pressure electro-deposition as anode, and electro-deposition product is cleaned by organic matter, removes ionic liquid Body obtains the Co for having silicon layer to surface3O4Nano wire finally carries out surface spray C processing, and dry, negative electrode tab is made in tabletting；
(5) positive plate, diaphragm, negative electrode tab are sequentially overlapped, the volume heart is made, is sealed in battery case, inject electrolyte, in advance It fills, aging, chemical conversion, lithium ion battery is made.
2. a kind of preparation method of lithium ion battery as described in claim 1, it is characterised in that: in step (1), the poly- phosphorus The additional amount of hydrochlorate is the 5-10% of phosphorus source, source of iron and glucose total weight.
3. a kind of preparation method of lithium ion battery as described in claim 1, it is characterised in that: the tool of low-kappa number nickel foam Gymnastics as: nickel foam is impregnated into 5min in 30% aqueous solution of nitric acid.
4. a kind of preparation method of lithium ion battery as described in claim 1, it is characterised in that: in step (1), mixed solution The adding speed of B and precipitant solution is respectively as follows: 1-5 ls/h, 0.8-2.6 ls/h.
5. a kind of preparation method of lithium ion battery as described in claim 1, it is characterised in that: in step (3), the mixing The preparation method of liquid specifically: 1-3g cobalt nitrate, 0.3-0.5g ammonium fluoride and 1-3g urea are dissolved in 50mL distilled water, delayed Slow stirring 30min.
6. a kind of preparation method of lithium ion battery as described in claim 1, it is characterised in that: in step (3), the heating The temperature of reaction is 110-130 DEG C, and the time of reaction is 1-5h.
7. a kind of preparation method of lithium ion battery as described in claim 1, it is characterised in that: in step (3), the high temperature The condition of calcining are as follows: calcine 1-4h at 350-450 DEG C.
8. a kind of preparation method of lithium ion battery as described in claim 1, it is characterised in that: in step (4), the constant pressure The condition of electro-deposition are as follows: with the Co of the direct growth nickel foam of preparation3O4Nano-wire array is as cathode, and Pt net electrode is as lazy Property anode, 50 DEG C contain 0.25M SiCl4Quaternary ammonium salt ionic liquid in silicon electrolyzation, constant voltage is -2.4V, and the time is 1-5h。
9. a kind of preparation method of lithium ion battery as described in claim 1, it is characterised in that: in step (5), the diaphragm It is to be mixed by nano aluminium oxide and micrometer alumina and pore creating material, secondary high-temperature is sintered multiaperture pellumina obtained, thick Degree is 80-120 μm, pore size 100-300nm.
10. a kind of preparation method of lithium ion battery as described in claim 1, it is characterised in that: in step (2), the height The temperature of temperature sintering is 720-960 DEG C, time 30-120min.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1431147A (en) * 2003-02-17 2003-07-23 郑绵平 Wet chemistry method for preparing lithium iron phosphate
CN102088080A (en) * 2011-01-07 2011-06-08 中南大学 Method for preparing phosphate series lithium ion battery anode material
CN104051728A (en) * 2014-05-22 2014-09-17 北京化工大学 Material with surface multilevel nano micron structure, preparation method thereof and nickel-zinc cell containing the material in anode
CN104681299A (en) * 2015-03-27 2015-06-03 吉林化工学院 Supercapacitor electrode material of cobaltosic oxide porous nanowire array, and preparation method thereof
CN105206833A (en) * 2015-08-31 2015-12-30 无锡市嘉邦电力管道厂 Preparing method for composite phosphate series lithium ion battery anode material
CN105896000A (en) * 2016-04-20 2016-08-24 浙江大学 Co3O4/CNT/MnO2 array electrode of core-shell structure as well as preparation method and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1431147A (en) * 2003-02-17 2003-07-23 郑绵平 Wet chemistry method for preparing lithium iron phosphate
CN102088080A (en) * 2011-01-07 2011-06-08 中南大学 Method for preparing phosphate series lithium ion battery anode material
CN104051728A (en) * 2014-05-22 2014-09-17 北京化工大学 Material with surface multilevel nano micron structure, preparation method thereof and nickel-zinc cell containing the material in anode
CN104681299A (en) * 2015-03-27 2015-06-03 吉林化工学院 Supercapacitor electrode material of cobaltosic oxide porous nanowire array, and preparation method thereof
CN105206833A (en) * 2015-08-31 2015-12-30 无锡市嘉邦电力管道厂 Preparing method for composite phosphate series lithium ion battery anode material
CN105896000A (en) * 2016-04-20 2016-08-24 浙江大学 Co3O4/CNT/MnO2 array electrode of core-shell structure as well as preparation method and application thereof

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