CN105633402A - Composite cathode material and preparation method thereof and lithium-ion battery - Google Patents

Composite cathode material and preparation method thereof and lithium-ion battery Download PDF

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Publication number
CN105633402A
CN105633402A CN201610134832.1A CN201610134832A CN105633402A CN 105633402 A CN105633402 A CN 105633402A CN 201610134832 A CN201610134832 A CN 201610134832A CN 105633402 A CN105633402 A CN 105633402A
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lithium
positive pole
lialo
composite positive
limnpo
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罗绍华
张俊
王志远
包硕
刘延国
王庆
张亚辉
刘思宁
李俊哲
刘东芳
孙梅竹
杨悦
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Northeastern University China
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Northeastern University China
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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
    • H01M4/58—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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention provides a composite cathode material and a preparation method thereof and a lithium-ion battery. The composite cathode material comprises lithium aluminate, lithium manganese phosphate and trace carbon, wherein the lithium manganese phosphate is loaded on the surface of the lithium aluminate; the mass of the lithium aluminate accounts for 0.1-10wt% that of the lithium manganese phosphate; the lithium aluminate is a hexagonal sheet of which the dimension is 5-10microns; the crystalline phase of the lithium aluminate is alpha-LiAlO<2>; and the lithium manganese phosphate is in a columnar or near-spherical form with the primary particle sizes of 50-200nm. With an LiAlO<2> porous nanosheet fast-ion conductor as the composite material, the cycle performance and the safety performance of the composite cathode material as a cathode of the lithium-ion battery are significantly improved; the preparation method of the composite cathode material is simple, low in cost, high in yield and the like; the process is easy to control; and LiMnPO<4> can be evenly compounded with the LiAlO<2>, so that a novel method is provided for preparation of the lithium manganese phosphate composite cathode material.

Description

A kind of composite positive pole, its preparation method and lithium ion battery
Technical field
The invention belongs to electrochemical material technical field, it relates to a kind of composite positive pole, its preparation method and lithium ion battery, particularly relate to a kind of LiAlO2-LiMnPO4/ C composite positive pole, its preparation method and comprise the lithium ion battery of described composite positive pole.
Background technology
Power lithium-ion battery is the core component of current electromobile, and energy density, high rate performance, cost, security and cycle life weigh the business-like key index of positive electrode material. At present business-like positive electrode material mainly contains ternary material battery, lithium manganate battery and ferric phosphate lithium cell, and this three classes positive electrode material does not have absolute predominance at this in five and causes the development of power lithium-ion battery material bottleneck occur. Though three component system battery material energy density height, on the high side, and to environment and technical requirements height in technique, thermostability is poor, there is bigger potential safety hazard; Lithium manganate battery price is relatively cheap, but its high temperature circulation difference is navigated in causing, reduction problem slowly highlights; Ferric phosphate lithium cell has extended cycle life, but energy density is low, causes iron lithium phosphate electromobile continual mileage shorter. To sum up, it is contemplated that to influence factors such as high temperature performance, cycle life, price and securities, currently business-like three kinds of batteries all can not become the ideal chose of following pure electric vehicle. Therefore, research and development are of future generation has the certainty that more high-energy-density, long lifetime, cheapness and safe new type power anode material for lithium-ion batteries are development.
In current reported positive electrode material, manganese-lithium phosphate anode material has the noble potential of 4.1V, improves 0.7V than iron lithium phosphate, and the energy density of lithium manganese phosphate battery is iron lithium phosphate improve about 20%, about 170Wh kg relatively-1, and lithium manganese phosphate cheaper. Compared with lithium manganate, lithium manganese phosphate has close operating voltage, but energy density is higher, and high-temperature cycle life is longer. Compared with ternary material, lithium manganese phosphate has similar energy density, but safer, price is lower. Therefore the concern widely that the research of manganese-lithium phosphate anode material causes.
But, electronics and the ionic conductivity of manganese-lithium phosphate anode material are poor, cause its high rate charge-discharge poor-performing. In recent years, coated by surfacing particle nanometer, ion doping, carbon or metal and lithium-containing oxides is coated etc. that means obviously improve LiMnPO4Chemical property. Such as, CN102931400A discloses a kind of nano-scale lithium ion battery composite positive pole LiMnPO4The synthetic method of/C; CN103000888A discloses a kind of lithium ion battery composite cathode material LiMnPO4-Li3V2(PO4)3/ C and its preparation method; CN103199247A discloses the preparation method of a kind of lithium ion battery composite cathode material with multi-level conductive network; CN103337628A discloses the synthetic method of a kind of positive material nano lithium manganese phosphate of lithium ion battery; CN101944597A discloses the preparation method of the coated LiMnPO4/C of a kind of charcoal-aero gel; CN104091946A discloses a kind of solvent and the method for carbon source integration synthesis LiMnPO4/C; CN103515599A discloses the preparation method of a kind of lithium manganese phosphate and carbon nanotube composite materials.
There is the LiAlO of nanometer laminated structure2It is a kind of fast-ionic conductor, there is high specific surface area and lithium ion conductive, lithium ion diffusion admittance can be provided, reduce lithium ion the evolving path. CN104241636A discloses a kind of Surface coating LiAlO2Lithium ion battery manganese system positive electrode material and its preparation method.
But, by LiAlO2With LiMnPO4Compound is used as positive electrode material, and need research further.
Summary of the invention
For the deficiency that prior art exists, it is an object of the invention to provide a kind of composite positive pole, its preparation method and lithium ion battery, described composite positive pole adopts lithium aluminate porous nano-sheet fast-ionic conductor to be matrix material, it significantly improves as cycle performance and the safety performance of lithium ion cell positive, it is possible to be widely used in field of lithium ion battery.
For reaching this object, the present invention by the following technical solutions:
If no special instructions, described " wt.% " all refers to mass percentage, and described composite positive pole can use LiAlO2-LiMnPO4/ C represents.
An object of the present invention is to provide a kind of composite positive pole, and described composite positive pole comprises lithium aluminate (LiAlO2) and lithium manganese phosphate (LiMnPO4) and the carbon (C) of trace, described lithium manganese phosphate load is on lithium aluminate surface, and the quality of described lithium aluminate accounts for the 0.1-10wt.% of lithium manganese phosphate quality, and described lithium aluminate to be size size the be hexagon sheet of 5-10 ��m, its crystalline phase is ��-LiAlO2; Column or the class of described lithium manganese phosphate to be granular size be 50-200nm are spherical.
Described size size refers to length and width and high size; A described granular size refers to grain size.
The lithium manganese phosphate of the nanoscale of compound lithium aluminate shortens Li+The evolving path, it is to increase Li+Embedding/deviate from speed, it is to increase the ionic conductivity of described composite positive pole.
The quality of described lithium aluminate accounts for the 0.1-10wt.% of lithium manganese phosphate quality, such as 0.2wt.%, 0.3wt.%, 0.5wt.%, 0.8wt.%, 1wt.%, 1.2wt.%, 1.5wt.%, 1.8wt.%, 2wt.%, 2.01wt.%, 2.5wt.%, 2.9wt.%, 3wt.%, 3.2wt.%, 3.5wt.%, 3.8wt.%, 4wt.%, 4.01wt.%, 4.3wt.%, 4.5wt.%, 4.8wt.%, 5.0wt.%, 5.01wt.%, 5.9wt.%, 6wt.%, 6.01wt.%, 6.5wt.%, 6.9wt.%, 7wt.%, 7.5wt.%, 7.9wt.%, 8wt.%, 8.01wt.%, 8.5wt.%, 9wt.% or 9.5wt.% etc.
The granular size of described lithium aluminate is 5-10 ��m, such as 6 ��m, 7 ��m, 8 ��m or 9 ��m etc.; Described lithium manganese phosphate is of a size of 50-200nm, such as 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 130nm, 140nm, 150nm, 160nm, 170nm, 180nm or 190nm etc.
The content that described " carbon of trace " means carbon is little, and described carbon is prepare in the process of described composite positive pole the carbon introduced, and its content is the 0.5-2wt.% of described composite positive pole quality.
Described composite positive pole (LiAlO2-LiMnPO4/ C) adopt LiAlO2Porous nano-sheet fast-ionic conductor is composite material compositions, LiMnPO4Load is at LiAlO2Porous matrix surface, it is all significantly increased as cycle performance and the safety performance of lithium ion cell positive.
The two of the object of the present invention are to provide the preparation method of a kind of composite positive pole as above, and described method comprises the steps:
(1) phosphoric acid solution is dripped in lithium hydroxide solution, it is precipitated product; Precipitated product is washed, and vacuum-drying, calcining, obtains canescence phosphoric acid powder for lithium;
(2) manganous sulfate and Trilithium phosphate are joined in the mixed solution of polyoxyethylene glycol and water, obtain mixture;
(3) lithium aluminate of formula ratio is joined in mixture, carry out hydro-thermal reaction, obtain hydro-thermal reaction product, wherein, the shape looks of lithium aluminate to be size size the be hexagon sheet of 5-10 ��m, crystalline phase is �� crystalline phase;
(4) hydro-thermal reaction product is washed, dry, obtain the presoma of lithium aluminate compound phosphoric acid manganese lithium;
(5) presoma by lithium aluminate compound phosphoric acid manganese lithium carries out bag carbon process, calcines, obtain described composite positive pole at 500-700 DEG C.
Hydrothermal method prepares described composite positive pole (LiAlO2-LiMnPO4/ C), it may be possible to provide high temperature and high pressure environment, it is ensured that the matrix material of generation is nanoscale.
The concentration of step (1) described phosphoric acid solution is 0.5-3.0mol/L, such as 0.6mol/L, 0.7mol/L, 0.8mol/L, 1.0mol/L, 1.5mol/L, 2.0mol/L, 2.5mol/L or 2.8mol/L etc.
Preferably, the concentration of step (1) described lithium hydroxide is 1.0-3.0mol/L, such as 1.2mol/L, 1.5mol/L, 1.8mol/L, 2.0mol/L, 2.2mol/L, 2.5mol/L or 2.8mol/L etc.
Preferably, step (1) described phosphoric acid solution drips in lithium hydroxide solution with the flow rate of 1.5-5mL/min, if flow rate is 1.6mL/min, 1.7mL/min, 1.8mL/min, 2.0mL/min, 2.2mL/min, 2.5mL/min, 2.8mL/min, 3.0mL/min, 3.5mL/min, 4.0mL/min or 4.5mL/min etc.
Preferably, the temperature of step (1) described calcining is 150-300 DEG C, and such as 160 DEG C, 180 DEG C, 200 DEG C, 220 DEG C, 230 DEG C, 250 DEG C or 280 DEG C etc., the time of calcining is 2-5h, such as 2.5h, 3h, 3.5h, 4h or 4.5h etc.
Preferably, the ratio of the amount of substance of step (2) described manganous sulfate and Trilithium phosphate is (1.5-3.5): 1, such as 1.8:1,2.0:1,2.5:1,3.0:1 or 3.2:1 etc.
Preferably, the volume ratio of step (2) described polyoxyethylene glycol and water is (0.5-4): 2, such as 0.8:2,1.0:2,1.2:2,1.5:2,1.8:2,2.0:2,2.5:2,3.0:2,3.5:2 or 3.8:2 etc.
Preferably, step (2) described polyoxyethylene glycol is the combination of any one or at least two kinds in PEG400, PEG800 or PEG2000. Typical but non-limiting combination is such as PEG400 and PEG800, PEG400 and PEG2000, PEG400, PEG800 and PEG2000.
Step (3) described lithium aluminate is with AAO template and Li2CO3For raw material prepares through hydrothermal method.
Preferably, the described lithium aluminate matrix of step (3) carries out vigorous stirring, described vigorous stirring after joining in mixture. Described vigorous stirring carries out on the agitator with shelves position, selects high tap position during stirring.
Preferably, the temperature of step (3) described hydro-thermal reaction is 165-200 DEG C, such as 170 DEG C, 175 DEG C, 180 DEG C, 190 DEG C or 195 DEG C etc., the time of hydro-thermal reaction is 6-24h, such as 7h, 8h, 9h, 10h, 12h, 13h, 15h, 18h, 20h or 22h etc.
Preferably, step (4) described drying is vacuum-drying.
Preferably, the described bag carbon of step (5) is treated to: mixed in dehydrated alcohol with carbon source by the presoma of lithium aluminate compound phosphoric acid manganese lithium, pulverizes, dry, calcining.
Preferably, described carbon source is the combination of any one or at least two kinds in xitix, glucose, sucrose, citric acid, oxyacetic acid, succsinic acid, PVA (polyvinyl alcohol), ethylene glycol or polyoxyethylene glycol. Typical but non-limiting combination is such as xitix and glucose, glucose and sucrose, ethylene glycol and polyoxyethylene glycol, sucrose, citric acid and oxyacetic acid, glucose, sucrose and citric acid, succsinic acid, PVA, ethylene glycol and polyoxyethylene glycol.
Preferably, the described presoma of lithium aluminate compound phosphoric acid manganese lithium is than 1:(0.15-0.35 with the mass ratio of carbon source), such as 1:0.18,1:0.19,1:0.20,1:0.22,1:0.25,1:0.28,1:0.30,1:0.32 or 1:0.34 etc.
Preferably, described pulverizing is: the presoma of lithium aluminate compound phosphoric acid manganese lithium is carried out ball milling, and the ball milling time is 2-6h, such as 2.5h, 3h, 3.5h, 4h, 4.5h, 5h or 5.5h etc.
Preferably, the temperature of described drying is 50-100 DEG C, and such as 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 95 DEG C etc., the dry time is 8-24h, such as 9h, 10h, 11h, 13h, 15h, 18h, 20h or 22h etc.
Preferably, described roasting carries out in an inert atmosphere, it is preferable to carry out in nitrogen atmosphere or argon gas atmosphere.
Preferably, the temperature of described calcining is 500-700 DEG C, such as 520 DEG C, 530 DEG C, 540 DEG C, 550 DEG C, 580 DEG C, 600 DEG C, 630 DEG C, 650 DEG C or 680 DEG C etc., the time of calcining is 3-10h, such as 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 7h, 8h or 9h etc.
As preferred technical scheme, the preparation method of described composite positive pole comprises the steps:
(1) by the H of 0.5-3.0mol/L3PO4Solution drips into the LiOH H of concentration as 1.0-3.0mol/L taking the flow rate of 1.5-5mL/min2In O solution, it is precipitated product; Precipitated product is washed, and vacuum-drying, sieves, at 150-300 DEG C, calcine 2-5h afterwards, obtain canescence Li3PO4Powder body;
(2) by (1.5-3.5): the amount of substance of 1 takes MnSO4��H2O and Li3PO4Powder body, is dissolved in volume ratio for (0.5-4): the PEG400-H of 22In O mixing solutions, obtain mixture;
(3) in mixture, add the LiAlO of formula ratio2, it is transferred in reactor by after mixing solutions vigorous stirring, after reacting 6-24h at 165-200 DEG C in homogeneous reactor, it is cooled to room temperature, obtain hydro-thermal reaction product;
(4) being washed by hydro-thermal reaction product, vacuum-drying, sieves, and obtains LiAlO2-LiMnPO4Presoma;
(5) by LiAlO2-LiMnPO4Presoma with xitix with mass ratio 1:(0.15-0.35) ratio fully mixes in dehydrated alcohol, ball milling 2-6h, dry 8-24h at 50-100 DEG C, then calcines 3-10h under 500-700 DEG C of nitrogen atmosphere, obtains LiAlO after naturally cooling2-LiMnPO4/ C composite.
The three of the object of the present invention are to provide the preparation method of another kind of composite positive pole described above, and described method comprises the steps:
(1) in the solution containing lithium source, manganese source and phosphorus source, add complexing agent, add the lithium aluminate of formula ratio afterwards, obtain mixing solutions, mixing solutions is made wet gel, wherein, lithium aluminate is size size is 5-10 ��m of hexagon sheet, and crystalline phase is �� crystalline phase;
(2) by wet gel ageing, dry, obtain xerogel;
(3) by xerogel precalcining, carry out two calcinings afterwards, obtain described composite positive pole.
The present invention adopts sol-gel method to prepare described composite positive pole, has that technique is simple, process is easily controlled, cost is low, product rate advantages of higher, it is possible to make LiMnPO4With LiAlO2Even compound is preparation LiMnPO4Composite positive pole provides novel method.
The mol ratio of Li, Mn and P in the described lithium source of step (1), manganese source and phosphorus source is (1-1.5): 1:1, such as 1.1:1:1,1.2:1:1,1.3:1:1 or 1.4:1:1 etc.
Preferably, the add-on of step (1) described complexing agent be the molar weight sum of manganese in the molar weight of lithium in lithium source and manganese source 1-3 doubly, such as 1.1 times, 1.5 times, 1.8 times, 2 times, 2.2 times, 2.5 times or 2.8 times etc.
Preferably, step (1) described wet gel is by stirring mixing solutions at 70-90 DEG C of condition lower magnetic force, and evaporating solns obtains, and described temperature can be 72 DEG C, 75 DEG C, 78 DEG C, 80 DEG C, 82 DEG C, 85 DEG C or 88 DEG C etc.
Preferably, step (1) described wet gel is sticky thick green colloidal sol.
The described lithium source of step (1) is the combination of any one or at least two kinds in lithium hydroxide, Quilonum Retard or lithium acetate, typical but non-limiting combination can be: lithium hydroxide and Quilonum Retard, lithium hydroxide and lithium acetate, Quilonum Retard and lithium acetate, lithium hydroxide, Quilonum Retard and lithium acetate.
Preferably, the described manganese source of step (1) is manganous sulfate and/or manganous acetate.
Preferably, the described phosphorus source of step (1) is phosphoric acid and/or primary ammonium phosphate.
Preferably, step (1) described complexing agent is any one or two or more combination in citric acid, oxyacetic acid, succsinic acid, ethylene glycol or polyoxyethylene glycol. Typical but non-limiting combination can be: citric acid and oxyacetic acid, citric acid and succsinic acid, ethylene glycol and polyoxyethylene glycol (PEG), oxyacetic acid, succsinic acid and ethylene glycol, citric acid, oxyacetic acid, succsinic acid, ethylene glycol and polyoxyethylene glycol.
Preferably, step (1) described water is deionized water.
Preferably, step (1) described lithium aluminate prepares by raw material of AAO template through hydrothermal method.
The temperature of the described wet gel ageing of step (2) is 10-35 DEG C, such as 12 DEG C, 15 DEG C, 18 DEG C, 20 DEG C, 22 DEG C, 25 DEG C, 28 DEG C, 30 DEG C or 32 DEG C etc.
Preferably, the time of the described wet gel ageing of step (2) is 10-24h, such as 12h, 13h, 15h, 18h, 20h or 22h etc.
Preferably, the temperature of step (2) described drying is 80-120 DEG C, such as 82 DEG C, 85 DEG C, 88 DEG C, 90 DEG C, 95 DEG C, 98 DEG C, 100 DEG C, 102 DEG C, 105 DEG C, 110 DEG C or 115 DEG C etc.
Preferably, the time of step (2) described drying is 5-15h, such as 8h, 10h, 12h, 13h or 14h etc.
Also pulverize before the described xerogel precalcining of step (3).
Preferably, the temperature of step (3) described precalcining is 300-400 DEG C, such as 320 DEG C, 330 DEG C, 340 DEG C, 350 DEG C, 360 DEG C, 370 DEG C, 380 DEG C or 390 DEG C etc.
Preferably, the time of step (3) described precalcining is 2-5h, such as 2.5h, 3h, 3.5h, 4h or 4.5h etc.
Preferably, step (3) described precalcining carries out under inert atmosphere or reducing atmosphere.
Preferably, the mixed atmosphere of any one or at least two kind of step (3) described precalcining in nitrogen atmosphere, argon gas atmosphere or hydrogen atmosphere carries out. The combination of typical but non-limiting calcination atmosphere can be: nitrogen atmosphere and argon gas atmosphere, nitrogen atmosphere and hydrogen atmosphere, nitrogen atmosphere, argon gas atmosphere and hydrogen atmosphere.
The temperature of described two calcinings of step (3) is 500-650 DEG C, such as 510 DEG C, 520 DEG C, 530 DEG C, 540 DEG C, 550 DEG C, 580 DEG C, 600 DEG C, 620 DEG C or 640 DEG C etc.
Preferably, the time of described two calcinings of step (3) is 5-10h, such as 6h, 7h, 8h or 9h etc.
Preferably, the product after described two calcinings of step (3), through cooling, obtains described composite positive pole after pulverizing. Those skilled in the art can select the temperature of cooling and the granularity of pulverizing according to the actual needs.
As preferred technical scheme, the preparation method of described composite positive pole comprises the steps:
(1) to the aqueous solution containing lithium source, manganese source and phosphorus source, add complexing agent, add the lithium aluminate of formula ratio afterwards, obtain mixing solutions, being stirred at 70-90 DEG C of condition lower magnetic force by mixing solutions, evaporating solns obtains wet gel, wherein, the mol ratio of Li, Mn and P in described lithium source, manganese source and phosphorus source is (1-1.5): 1:1, the add-on of described complexing agent be the molar weight sum of manganese in the molar weight of lithium in lithium source and manganese source 1-3 doubly;
(2) by wet gel at 10-35 DEG C of ageing 10-24h, afterwards at 80-120 DEG C of dry 5-15h, pulverize, obtain dry gel powder;
(3) by dry gel powder at 300-400 DEG C of precalcining 2-5h, two calcinings under inert atmosphere or reducing atmosphere afterwards, the temperature of two calcinings is 500-650 DEG C, and the time of two calcinings is 5-10h, calcinate, through pulverizing, obtains the mixture of described lithium aluminate and lithium manganese phosphate.
Present invention also offers the purposes of composite positive pole described above, it is for anode material for lithium-ion batteries.
Compared with prior art, the useful effect of the present invention is:
(1) composite positive pole (LiAlO provided by the invention2-LiMnPO4/ C) adopt LiAlO2Porous nano-sheet fast-ionic conductor is matrix material, and lithium manganese phosphate load is at LiAlO2Porous matrix surface, it is all significantly increased as cycle performance (first discharge specific capacity of described composite positive pole can reach 151.2mAh/g, circulates 50 times, and capability retention is 95.3%) and the safety performance of lithium ion cell positive.
(2) composite positive pole (LiAlO provided by the invention2-LiMnPO4/ C) preparation method have that technique is simple, process is easily controlled, cost is low, product rate advantages of higher, it is possible to make LiMnPO4With LiAlO2Even compound, provides novel method for preparing lithium manganese phosphate composite positive pole.
Accompanying drawing explanation
Fig. 1 is LiAlO in embodiment 12-LiMnPO4The XRD figure of/C composite positive pole.
Fig. 2 is LiAlO in embodiment 12-LiMnPO4The SEM figure of/C composite positive pole.
Fig. 3 is LiAlO in embodiment 22-LiMnPO4The XRD figure of/C composite positive pole.
Fig. 4 is LiAlO in embodiment 22-LiMnPO4The SEM figure of/C composite positive pole.
Fig. 5 is LiAlO in embodiment 32-LiMnPO4The XRD figure of/C composite positive pole.
Fig. 6 is LiAlO in embodiment 32-LiMnPO4The SEM figure of/C composite positive pole.
Fig. 7 is LiAlO in embodiment 42-LiMnPO4The XRD figure of/C composite positive pole.
Fig. 8 is LiAlO in embodiment 42-LiMnPO4The SEM figure of/C composite positive pole.
Fig. 9 is LiAlO in embodiment 52-LiMnPO4The XRD figure of/C composite positive pole.
Figure 10 is LiAlO in embodiment 52-LiMnPO4The SEM figure of/C composite positive pole.
Figure 11 is LiAlO in embodiment 62-LiMnPO4The XRD figure of/C composite positive pole.
Figure 12 is LiAlO in embodiment 62-LiMnPO4The SEM figure of/C composite positive pole.
Figure 13 is LiAlO in embodiment 72-LiMnPO4The XRD figure of/C composite positive pole.
Figure 14 is LiAlO in embodiment 72-LiMnPO4The SEM figure of/C composite positive pole.
Figure 15 is LiAlO in embodiment 82-LiMnPO4The XRD figure of/C composite positive pole.
Figure 16 is LiAlO in embodiment 82-LiMnPO4The SEM figure of/C composite positive pole.
Figure 17 is LiAlO in embodiment 92-LiMnPO4The XRD figure of/C composite positive pole.
Figure 18 is LiAlO in embodiment 92-LiMnPO4The SEM figure of/C composite positive pole.
Figure 19 is LiAlO in embodiment 102-LiMnPO4The XRD figure of/C composite positive pole.
Figure 20 is LiAlO in embodiment 102-LiMnPO4The SEM figure of/C composite positive pole.
Figure 21 is LiAlO in embodiment 112-LiMnPO4The XRD figure of/C composite positive pole.
Figure 22 is LiAlO in embodiment 112-LiMnPO4The SEM figure of/C composite positive pole.
Embodiment
Below in conjunction with accompanying drawing and the technical scheme of the present invention is described further by embodiment. Performance data in following examples is all at 25 DEG C, and 0.05C records, and testing tool is LandCT2001A cell tester, and voltage tester scope is 2.5V-4.5V.
Embodiment 1
A kind of LiAlO2-LiMnPO4/ C composite positive pole, described composite positive pole comprises the carbon of lithium aluminate, lithium manganese phosphate and trace, and described lithium manganese phosphate load is on described lithium aluminate surface, and the quality of described lithium aluminate accounts for the 1wt.% of described lithium manganese phosphate quality; Described lithium aluminate to be size size the be sheet-shaped looks of hexagon of 7-10 ��m, its crystalline phase is ��-LiAlO2; The class of described lithium manganese phosphate to be granular size be 180-200nm is spherical, and a described particle agglomeration forms time micron ball.
Described LiAlO2-LiMnPO4The preparation method of/C composite positive pole comprises the steps:
(1) by the H of 0.5mol/L3PO4Solution drips into the LiOH H of concentration as 1.0mol/L taking the flow rate of 5mL/min2In O solution, it is precipitated product; Precipitated product is washed, and vacuum-drying, sieve, at 300 DEG C, calcine 5h afterwards, obtain canescence Li3PO4Powder body;
(2) MnSO is got4��H2The Li of O and above-mentioned steps synthesis3PO4With the amount of substance of 3:1 than the PEG400-H being dissolved in 1:2 volume ratio2In O mixing solutions, obtain mixture;
(3) adding the mass ratio accounting for lithium manganese phosphate in mixture is the LiAlO of 1wt.%2Matrix, after vigorous stirring, is transferred in reactor, after reacting 6h, is cooled to room temperature, obtains hydrothermal product in homogeneous reactor at 190 DEG C;
(4) hydrothermal product is washed, and vacuum-drying, sieve, obtain LiAlO2-LiMnPO4Presoma;
(5) by LiAlO2-LiMnPO4Presoma fully mixes with mass ratio 1:0.25 ratio with xitix in a little dehydrated alcohol, ball milling 2h, dry 8h at 100 DEG C, then calcines 3h under 550 DEG C of nitrogen atmospheres, obtains LiAlO after naturally cooling2-LiMnPO4/ C composite.
To obtained LiAlO2-LiMnPO4/ C composite positive pole carries out X-ray diffraction (XRD) test and scanning electron microscope (SEM) test, and test result is as depicted in figs. 1 and 2. As can be seen from the figure, product is the LiMnPO of the olivine structural of pure phase4, shape looks are the secondary micron ball that the spherical primary particle of class is reunited.
By described LiAlO2-LiMnPO4/ C composite positive pole is made into lithium ion cell positive, tests its cycle performance and capacity, and test result is under 0.05C, and first discharge specific capacity is 144.0mAh/g, circulates 50 times, and capability retention is 94.1%.
Embodiment 2
A kind of LiAlO2-LiMnPO4/ C composite positive pole, described composite positive pole comprises the carbon of lithium aluminate, lithium manganese phosphate and trace, and described lithium manganese phosphate load is on described lithium aluminate surface, and the quality of described lithium aluminate accounts for the 2wt.% of described lithium manganese phosphate quality; Described lithium aluminate to be size size the be hexagon sheet of 5-7 ��m, its crystalline phase is ��-LiAlO2; The class of described lithium manganese phosphate to be granular size be 100-130nm is spherical, and the spherical primary particle of described class is reunited and formed time micron ball.
Described LiAlO2-LiMnPO4The preparation method of/C composite positive pole comprises the steps:
(1) by the H of 1.5mol/L3PO4Solution drips into the LiOH H of concentration as 3.0mol/L taking the flow rate of 1.5mL/L2In O solution, it is precipitated product; Precipitated product is washed, and vacuum-drying, sieve, at 150 DEG C, calcine 2h afterwards, obtain canescence Li3PO4Powder body;
(2) MnSO is got4��H2The Li of O and above-mentioned steps synthesis3PO4With the amount of substance of 1.5:1 than the PEG400-H being dissolved in 0.5:2 volume ratio2In O mixing solutions, obtain mixture;
(3) adding the mass ratio accounting for lithium manganese phosphate in mixture is the LiAlO of 2wt.%2Matrix, after vigorous stirring, is transferred in reactor, after reacting 18h, is cooled to room temperature, obtains hydrothermal product in homogeneous reactor at 180 DEG C;
(4) hydrothermal product is washed, and vacuum-drying, sieve, obtain LiAlO2-LiMnPO4Presoma;
(5) by LiAlO2-LiMnPO4Presoma fully mixes with mass ratio 1:0.35 ratio with xitix in a little dehydrated alcohol, ball milling 6h, and at 50 DEG C, dry 24h, calcines 5h under 700 DEG C of nitrogen atmospheres, obtain LiAlO after naturally cooling2-LiMnPO4/ C composite.
To obtained LiAlO2-LiMnPO4/ C composite positive pole carries out X-ray diffraction (XRD) test and scanning electron microscope (SEM) test, and test result is as shown in Figure 3 and Figure 4. As can be seen from the figure, product is the LiMnPO of the olivine structural of pure phase4, shape looks are the secondary micron ball that the spherical primary particle of class is reunited.
By described LiAlO2-LiMnPO4/ C composite positive pole is made into lithium ion cell positive, tests its cycle performance and capacity, and test result is under 0.05C, and first discharge specific capacity is 145.2mAh/g, circulates 50 times, and capability retention is 95.8%.
Embodiment 3
A kind of LiAlO2-LiMnPO4/ C composite positive pole, described composite positive pole comprises the carbon of lithium aluminate, lithium manganese phosphate and trace, described lithium manganese phosphate load is on described lithium aluminate surface, the quality of described lithium aluminate accounts for the 4wt.% of described lithium manganese phosphate quality, described lithium aluminate is size size is 6-8 ��m of hexagon sheet, and its crystalline phase is ��-LiAlO2; The class of described lithium manganese phosphate to be granular size be 50-120nm is spherical, and the spherical primary particle of described class is reunited and formed time micron ball.
Described LiAlO2-LiMnPO4The preparation method of/C composite positive pole comprises the steps:
(1) by the H of 2.0mol/L3PO4Solution drips into the LiOH H of concentration as 2.0mol/L taking the flow rate of 3.5mL/L2In O solution, it is precipitated product; Precipitated product is washed, and vacuum-drying, sieves, at 250 DEG C, calcine 3h afterwards, obtain canescence Li3PO4Powder body;
(2) MnSO is got4��H2The Li of O and above-mentioned steps synthesis3PO4With the amount of substance of 3:1 than the PEG400-H being dissolved in 1:2 volume ratio2In O mixing solutions, obtain mixture;
(3)) adding the mass ratio accounting for lithium manganese phosphate in mixture is the LiAlO of 4wt.%2Matrix, after vigorous stirring, is transferred in reactor, after reacting 10h, is cooled to room temperature, obtains hydrothermal product in homogeneous reactor at 170 DEG C;
(4) hydrothermal product is washed, and vacuum-drying, sieve, obtain LiAlO2-LiMnPO4Presoma;
(5) by LiAlO2-LiMnPO4Presoma fully mixes with mass ratio 1:0.25 ratio with xitix in a little dehydrated alcohol, ball milling 3h, and at 50 DEG C, dry 12h, calcines 3h under 550 DEG C of nitrogen atmospheres, obtain LiAlO after naturally cooling2-LiMnPO4/C composite.
To obtained LiAlO2-LiMnPO4/ C composite positive pole carries out X-ray diffraction (XRD) test and scanning electron microscope (SEM) test, and test result is as shown in Figure 5 and Figure 6. As can be seen from the figure product is the LiMnPO of the olivine structural of pure phase4, shape looks are the secondary micron ball that the spherical primary particle of class is reunited.
By described LiAlO2-LiMnPO4/ C composite positive pole is made into lithium ion cell positive, tests its cycle performance and capacity, and test result is under 0.05C, and first discharge specific capacity is 145.2mAh/g, circulates 50 times, and capability retention is 94.8%.
Embodiment 4
A kind of LiAlO2-LiMnPO4/ C composite positive pole, described composite positive pole comprises the carbon of lithium aluminate, lithium manganese phosphate and trace, described lithium manganese phosphate load is on described lithium aluminate surface, the quality of described lithium aluminate accounts for the 6wt.% of described lithium manganese phosphate quality, described lithium aluminate to be size size the be hexagon sheet of 7-10 ��m, its crystalline phase is ��-LiAlO2; The class of described lithium manganese phosphate to be granular size be 50-100nm is spherical, and the spherical primary particle of described class is reunited and formed time micron ball.
Described LiAlO2-LiMnPO4The preparation method of/C composite positive pole comprises the steps:
(1) by the H of 3mol/L3PO4Solution drips into the LiOH H of concentration as 1.5mol/L taking the flow rate of 2.5mL/min2In O solution, it is precipitated product; Precipitated product is washed, and vacuum-drying, sieves, at 250 DEG C, calcine 4h afterwards, obtain canescence Li3PO4Powder body;
(2) MnSO is got4��H2The Li of O and above-mentioned steps synthesis3PO4With the amount of substance of 3.5:1 than the PEG400-H being dissolved in 4:2 volume ratio2In O mixing solutions, obtain mixture;
(3) adding the mass ratio accounting for lithium manganese phosphate in mixture is the LiAlO of 6wt.%2Matrix, after vigorous stirring, is transferred in reactor, after reacting 8h, is cooled to room temperature, obtains hydrothermal product in homogeneous reactor at 165 DEG C;
(4) hydrothermal product is washed, and vacuum-drying, sieve, obtain LiAlO2-LiMnPO4Presoma;
(5) by LiAlO2-LiMnPO4Presoma fully mixes with mass ratio 1:0.15 ratio with xitix in a little dehydrated alcohol, ball milling 4h, and at 50 DEG C, dry 12h, calcines 10h under 500 DEG C of nitrogen atmospheres, obtain LiAlO after naturally cooling2-LiMnPO4/ C composite.
To obtained LiAlO2-LiMnPO4/ C composite positive pole carries out X-ray diffraction (XRD) test and scanning electron microscope (SEM) test, and test result is as shown in Figure 7 and Figure 8. As can be seen from the figure, product is the LiMnPO of the olivine structural of pure phase4, shape looks are the secondary micron ball that the spherical primary particle of class is reunited.
By described LiAlO2-LiMnPO4/ C composite positive pole is made into lithium ion cell positive, tests its cycle performance and capacity, and test result is under 0.05C, and first discharge specific capacity is 149.2mAh/g, circulates 50 times, and capability retention is 91.8%.
Embodiment 5
A kind of LiAlO2-LiMnPO4/ C composite positive pole, described composite positive pole comprises the carbon of lithium aluminate, lithium manganese phosphate and trace, described lithium manganese phosphate load is on described lithium aluminate surface, the quality of described lithium aluminate accounts for the 8wt.% of described lithium manganese phosphate quality, described lithium aluminate to be size size the be hexagon sheet of 6-10 ��m, its crystalline phase is ��-LiAlO2; The class of described lithium manganese phosphate to be granular size be 110-140nm is spherical, and the spherical primary particle of described class is reunited and formed time micron ball.
Described LiAlO2-LiMnPO4The preparation method of/C composite positive pole comprises the steps:
(1) by the H of 4mol/L3PO4Solution drips into the LiOH H of concentration as 2.5mol/L taking the flow rate of 1.5mL/min2In O solution, it is precipitated product; Precipitated product is washed, and vacuum-drying, sieves, at 280 DEG C, calcine 2h afterwards, obtain canescence Li3PO4Powder body;
(2) MnSO is got4��H2The Li of O and above-mentioned steps synthesis3PO4With the amount of substance of 3:1 than the PEG400-H being dissolved in 3:2 volume ratio2In O mixing solutions, obtain mixture;
(3)) adding the mass ratio accounting for lithium manganese phosphate in mixture is the LiAlO of 8wt.%2Matrix, after vigorous stirring, is transferred in reactor, after reacting 12h, is cooled to room temperature, obtains hydrothermal product in homogeneous reactor at 200 DEG C;
(4) hydrothermal product is washed, and vacuum-drying, sieve, obtain LiAlO2-LiMnPO4Presoma;
(5) by LiAlO2-LiMnPO4Presoma fully mixes with mass ratio 1:0.20 ratio with xitix in a little dehydrated alcohol, ball milling 3h, and at 80 DEG C, dry 12h, calcines 5h under 600 DEG C of nitrogen atmospheres, obtain LiAlO after naturally cooling2-LiMnPO4/ C composite.
To obtained LiAlO2-LiMnPO4/ C composite positive pole carries out X-ray diffraction (XRD) test and scanning electron microscope (SEM) test, and test result is as shown in Figure 9 and Figure 10. As can be seen from the figure, product is the LiMnPO of the olivine structural of pure phase4, shape looks are the secondary micron ball that the spherical primary particle of class is reunited.
By described LiAlO2-LiMnPO4/ C composite positive pole is made into lithium ion cell positive, tests its cycle performance and capacity, and test result is under 0.05C, and first discharge specific capacity is 143.1mAh/g, circulates 50 times, and capability retention is 90.4%.
Embodiment 6
A kind of LiAlO2-LiMnPO4/ C composite positive pole, described composite positive pole comprises the carbon of lithium aluminate, lithium manganese phosphate and trace, described lithium manganese phosphate load is on described lithium aluminate surface, the quality of described lithium aluminate accounts for the 10wt.% of described lithium manganese phosphate quality, described lithium aluminate to be size size the be hexagon sheet of 5-8 ��m, its crystalline phase is ��-LiAlO2; The class of described lithium manganese phosphate to be granular size be 130-160nm is spherical, and the spherical primary particle of described class is reunited and formed time micron ball.
Described LiAlO2-LiMnPO4The preparation method of/C composite positive pole comprises the steps:
(1) by the H of 1.0mol/L3PO4Solution drips into the LiOH H of concentration as 1.2mol/L taking the flow rate of 2.5mL/min2In O solution, it is precipitated product; Precipitated product is washed, and vacuum-drying, sieves, at 300 DEG C, calcine 3h afterwards, obtain canescence Li3PO4Powder body;
(2) MnSO is got4��H2The Li of O and above-mentioned steps synthesis3PO4With the amount of substance of 2.5:1 than the PEG400-H being dissolved in 1.5:2 volume ratio2In O mixing solutions, obtain mixture;
(3)) adding the mass ratio accounting for lithium manganese phosphate in mixture is the LiAlO of 10wt.%2Matrix, after vigorous stirring, is transferred in reactor, after reacting 24h, is cooled to room temperature, obtains hydrothermal product in homogeneous reactor at 170 DEG C;
(4) hydrothermal product is washed, and vacuum-drying, sieve, obtain LiAlO2-LiMnPO4Presoma;
(5) by LiAlO2-LiMnPO4Presoma fully mixes with mass ratio 1:0.25 ratio with xitix in a little dehydrated alcohol, ball milling 3h, and at 60 DEG C, dry 18h, calcines 4h under 650 DEG C of nitrogen atmospheres, obtain LiAlO after naturally cooling2-LiMnPO4/ C composite.
To obtained LiAlO2-LiMnPO4/ C composite positive pole carries out X-ray diffraction (XRD) test and scanning electron microscope (SEM) test, and test result is as is illustrated by figs. 11 and 12. As can be seen from the figure, product is the LiMnPO of the olivine structural of pure phase4, shape looks are the secondary micron ball that the spherical primary particle of class is reunited.
By described LiAlO2-LiMnPO4/ C composite positive pole is made into lithium ion cell positive, tests its cycle performance and capacity, and test result is under 0.05C, and first discharge specific capacity is 143.5mAh/g, circulates 50 times, and capability retention is 95.4%.
Embodiment 7
A kind of LiAlO2-LiMnPO4/ C composite positive pole, described composite positive pole comprises the carbon of lithium aluminate, lithium manganese phosphate and trace, described lithium manganese phosphate load is on described lithium aluminate surface, the quality of described lithium aluminate accounts for the 1wt.% of described lithium manganese phosphate quality, described lithium aluminate to be size size the be hexagon sheet of 5-8 ��m, its crystalline phase is ��-LiAlO2; Described lithium manganese phosphate is a granular size is that 50-100nm class is spherical, and the spherical primary particle of described class is reunited and formed micron ball.
Described LiAlO2-LiMnPO4The preparation method of/C composite positive pole comprises the steps:
(1) by lithium source, manganese source and phosphorus source Li:Mn:P=(1-1.5): 1:1 raw materials weighing in molar ratio, and add the solution forming equal one in deionized water, add the complexing agent of 1 times of metal ion molar weight, then add the LiAlO of the 1wt.% accounting for lithium manganese phosphate2Porous nano-sheet; Stir and evaporating solns at 90 DEG C of lower magnetic forces, obtain blackish green wet gel;
(2) ageing 24h at described wet gel being placed in 25 DEG C; 120 DEG C of dry 5h, obtain xerogel; After grinding, obtain dry gel powder;
(3) being processed in 300 DEG C of precalcinings under inert atmosphere or reducing atmosphere by dry gel powder body, insulation 3h, then 550 DEG C of two calcinings, insulation 10h, obtains LiAlO after grinding2-LiMnPO4/ C composite positive pole.
To obtained LiAlO2-LiMnPO4/ C composite positive pole carries out X-ray diffraction (XRD) test and scanning electron microscope (SEM) test, and test result is as shown in Figure 13 and Figure 14. As can be seen from the figure, it is the LiMnPO of olivine structural4Pure phase, shape looks be the spherical nanoscale of class a particle agglomeration together, the micron ball of formation.
By described LiAlO2-LiMnPO4/ C composite positive pole is made into lithium ion cell positive, tests its cycle performance and capacity, and test result is under 0.05C, and first discharge specific capacity is 144.6mAh/g, circulates 50 times, and capability retention is 90.6%.
Embodiment 8
A kind of LiAlO2-LiMnPO4/ C composite positive pole, described composite positive pole comprises the carbon of lithium aluminate, lithium manganese phosphate and trace, described lithium manganese phosphate load is on described lithium aluminate surface, the quality of described lithium aluminate accounts for the 3wt.% of described lithium manganese phosphate quality, described lithium aluminate to be size size the be hexagon sheet of 8-10 ��m, its crystalline phase is ��-LiAlO2; The class of described lithium manganese phosphate to be granular size be 100-120nm is spherical, and the spherical primary particle of described class is reunited and formed micron ball.
Described LiAlO2-LiMnPO4The preparation method of/C composite positive pole comprises the steps:
(1) by lithium source, manganese source and phosphorus source Li:Mn:P=(1-1.5): 1:1 raw materials weighing in molar ratio, and add the solution forming equal one in deionized water, add the complexing agent of 1.5 times of metal ion molar weights, then add the LiAlO of the 3wt.% accounting for lithium manganese phosphate2Porous nano-sheet; Stir and evaporating solns at 70 DEG C of lower magnetic forces, obtain wet gel;
(2) ageing 15h at being placed in 25 DEG C; 80 DEG C of dry 15h, obtain xerogel; After grinding, obtain dry gel powder;
(3) being processed in 400 DEG C of precalcinings under inert atmosphere or reducing atmosphere by dry gel powder body, insulation 2h, then 650 DEG C of two calcinings, insulation 5h, obtains LiAlO after grinding2-LiMnPO4/ C composite positive pole.
To obtained LiAlO2-LiMnPO4/ C composite positive pole carries out X-ray diffraction (XRD) test and scanning electron microscope (SEM) test, and test result is as shown in Figure 15 and Figure 16. As can be seen from the figure, it is the LiMnPO of olivine structural4Pure phase, shape looks be the spherical nanoscale of class a particle agglomeration together, the micron ball of formation.
By described LiAlO2-LiMnPO4/ C composite positive pole is made into lithium ion cell positive, tests its cycle performance and capacity, and test result is under 0.05C, and first discharge specific capacity is 145.7mAh/g, circulates 50 times, and capability retention is 93.8%.
Embodiment 9
A kind of LiAlO2-LiMnPO4/ C composite positive pole, described composite positive pole comprises the carbon of lithium aluminate, lithium manganese phosphate and trace, described lithium manganese phosphate load is on described lithium aluminate surface, the quality of described lithium aluminate accounts for the 5wt.% of described lithium manganese phosphate quality, described lithium aluminate to be size size the be hexagon sheet of 5-7 ��m, its crystalline phase is ��-LiAlO2; Described lithium manganese phosphate is a granular size is the column of 120-200nm, and described column primary particle is reunited and formed micron ball.
Described LiAlO2-LiMnPO4The preparation method of/C composite positive pole comprises the steps:
(1) by lithium source, manganese source and phosphorus source Li:Mn:P=(1-1.5): 1:1 raw materials weighing in molar ratio, and add the solution forming equal one in deionized water, add the complexing agent of 2 times of metal ion molar weights, then add the LiAlO of the 5wt.% accounting for lithium manganese phosphate2Porous nano-sheet; Stir and evaporating solns at 80 DEG C of lower magnetic forces, obtain wet gel;
(2) ageing 12h at being placed in 25 DEG C; 100 DEG C of dry 15h, obtain xerogel; After grinding, obtain dry gel powder;
(3) being processed in 350 DEG C of precalcinings under inert atmosphere or reducing atmosphere by dry gel powder body, insulation 3h, then 600 DEG C of two calcinings, insulation 8h, obtains LiAlO after grinding2-LiMnPO4/ C composite positive pole.
To obtained LiAlO2-LiMnPO4/ C composite positive pole carries out X-ray diffraction (XRD) test and scanning electron microscope (SEM) test, and test result is as shown in Figure 17 and Figure 18. As can be seen from the figure, it is the LiMnPO of olivine structural4Pure phase, shape looks are a particle of the nanoscale of column, in discrete distribution state.
By described LiAlO2-LiMnPO4/ C composite positive pole is made into lithium ion cell positive, tests its cycle performance and capacity, and test result is under 0.05C, and first discharge specific capacity is 151.2mAh/g, circulates 50 times, and capability retention is 95.3%.
Embodiment 10
A kind of LiAlO2-LiMnPO4/ C composite positive pole, described composite positive pole comprises the carbon of lithium aluminate, lithium manganese phosphate and trace, described lithium manganese phosphate load is on described lithium aluminate surface, the quality of described lithium aluminate accounts for the 7wt.% of described lithium manganese phosphate quality, described lithium aluminate to be size size the be sheet-shaped looks of hexagon of 5-10 ��m, its crystalline phase is ��-LiAlO2; The class of described lithium manganese phosphate to be granular size be 50-100nm is spherical, and the spherical primary particle of described class is reunited and formed micron ball.
Described LiAlO2-LiMnPO4The preparation method of/C composite positive pole comprises the steps:
(1) by lithium source, manganese source and phosphorus source Li:Mn:P=(1-1.5): 1:1 raw materials weighing in molar ratio, and add the solution forming equal one in deionized water, add the complexing agent of 2.5 times of metal ion molar weights, then add the LiAlO of the 7wt.% accounting for lithium manganese phosphate2Porous nano-sheet; Stir and evaporating solns at 75 DEG C of lower magnetic forces, obtain wet gel;
(2) ageing 18h at being placed in 25 DEG C; 80 DEG C of dry 12h, obtain xerogel; After grinding, obtain dry gel powder;
(3) being processed in 300 DEG C of precalcinings under inert atmosphere or reducing atmosphere by dry gel powder body, insulation 2h, then 600 DEG C of two calcinings, insulation 6h, obtains LiAlO after grinding2-LiMnPO4/ C composite positive pole.
To obtained LiAlO2-LiMnPO4/ C composite positive pole carries out X-ray diffraction (XRD) test and scanning electron microscope (SEM) test, and test result is as illustrated in figures 19 and 20. As can be seen from the figure, it is the LiMnPO of olivine structural4Pure phase, shape looks be the spherical nanoscale of class a particle agglomeration together, the micron ball of formation.
By described LiAlO2-LiMnPO4/ C composite positive pole is made into lithium ion cell positive, tests its cycle performance and capacity, and test result is under 0.05C, and first discharge specific capacity is 146.1mAh/g, circulates 50 times, and capability retention is 91.6%.
Embodiment 11
A kind of LiAlO2-LiMnPO4/ C composite positive pole, described composite positive pole comprises the carbon of lithium aluminate, lithium manganese phosphate and trace, described lithium manganese phosphate load is on described lithium aluminate surface, the quality of described lithium aluminate accounts for the 10wt.% of described lithium manganese phosphate quality, described lithium aluminate is size size is 5-10 ��m of hexagon sheet, and its crystalline phase is ��-LiAlO2; The class of described lithium manganese phosphate to be granular size be 80-120nm is spherical, and the spherical primary particle of described class is reunited and formed micron ball.
Described LiAlO2-LiMnPO4The preparation method of/C composite positive pole comprises the steps:
(1) by lithium source, manganese source and phosphorus source Li:Mn:P=(1-1.5): 1:1 raw materials weighing in molar ratio, and add the solution forming equal one in deionized water, add the complexing agent of 3 times of metal ion molar weights, then add the LiAlO of the 10wt.% accounting for lithium manganese phosphate2Porous nano-sheet; Stir and evaporating solns at 85 DEG C of lower magnetic forces, obtain wet gel;
(2) ageing 20h at being placed in 25 DEG C; 120 DEG C of dry 8h, obtain xerogel; After grinding, obtain dry gel powder;
(3) being processed in 400 DEG C of precalcinings under inert atmosphere or reducing atmosphere by dry gel powder body, insulation 3h, then 500 DEG C of two calcinings, insulation 10h, obtains LiAlO after grinding2-LiMnPO4/ C composite positive pole.
To obtained LiAlO2-LiMnPO4/ C composite positive pole carries out X-ray diffraction (XRD) test and surface sweeping Electronic Speculum (SEM) test, and test result is as shown in figure 21 and figure. As can be seen from the figure, it is the LiMnPO of olivine structural4Pure phase, shape looks be the spherical nanoscale of class a particle agglomeration together, the micron ball of formation.
By described LiAlO2-LiMnPO4/ C composite positive pole is made into lithium ion cell positive, tests its cycle performance and capacity, and test result is under 0.05C, and first discharge specific capacity is 145.9mAh/g, circulates 50 times, and capability retention is 92.5%.
Embodiment 12
A kind of LiAlO2-LiMnPO4/ C composite positive pole, described composite positive pole comprises the carbon of lithium aluminate, lithium manganese phosphate and trace, described lithium manganese phosphate load is on described lithium aluminate surface, the quality of described lithium aluminate accounts for the 0.1wt.% of described lithium manganese phosphate quality, described lithium aluminate is size size is 5-10 ��m of hexagon sheet, and its crystalline phase is ��-LiAlO2; The class of described lithium manganese phosphate to be granular size be 100-150nm is spherical, and the spherical primary particle of described class is reunited and formed micron ball.
Described LiAlO2-LiMnPO4The preparation method of/C composite positive pole comprises the steps:
(1) by lithium source, manganese source and phosphorus source Li:Mn:P=(1-1.5): 1:1 raw materials weighing in molar ratio, and add the solution forming equal one in deionized water, add the complexing agent of 1.2 times of metal ion molar weights, then add the LiAlO of the 0.1wt.% accounting for lithium manganese phosphate2Porous nano-sheet; Stir and evaporating solns at 80 DEG C of lower magnetic forces, obtain wet gel;
(2) ageing 15h at being placed in 25 DEG C; 120 DEG C of dry 8h, obtain xerogel; After grinding, obtain dry gel powder;
(3) being processed in 350 DEG C of precalcinings under inert atmosphere or reducing atmosphere by dry gel powder body, insulation 4h, then 550 DEG C of two calcinings, insulation 10h, obtains LiAlO after grinding2-LiMnPO4/ C composite positive pole.
By described LiAlO2-LiMnPO4/ C composite positive pole is made into lithium ion cell positive, tests its cycle performance and capacity, and test result is under 0.05C, and first discharge specific capacity is 146.6mAh/g, circulates 50 times, and capability retention is 92.1%.
Comparative example 1
A kind of composite positive pole and its preparation method, except the 11wt.% that the quality of lithium aluminate is lithium manganese phosphate quality, all the other are identical with embodiment 4.
By described LiAlO2-LiMnPO4/ C composite positive pole is made into lithium ion cell positive, tests its cycle performance and capacity, and test result is under 0.05C, and first discharge specific capacity is 110.2mAh/g, circulates 50 times, and capability retention is 64.8%.
Comparative example 2
A kind of composite positive pole and its preparation method, except the 0.05wt.% that the quality of lithium aluminate is lithium manganese phosphate quality, all the other are identical with embodiment 4.
By described LiAlO2-LiMnPO4/ C composite positive pole is made into lithium ion cell positive, tests its cycle performance and capacity, and test result is under 0.05C, and first discharge specific capacity is 108.9mAh/g, circulates 50 times, and capability retention is 59.8%.
Comparative example 3
A kind of composite positive pole and its preparation method, except the 11wt.% that the quality of lithium aluminate is lithium manganese phosphate quality, all the other are identical with embodiment 9.
By described LiAlO2-LiMnPO4/ C composite positive pole is made into lithium ion cell positive, tests its cycle performance and capacity, and test result is under 0.05C, and first discharge specific capacity is 115.2mAh/g, circulates 50 times, and capability retention is 80.6%.
Comparative example 4
A kind of composite positive pole and its preparation method, except the 0.05wt.% that the quality of lithium aluminate is lithium manganese phosphate quality, all the other are identical with embodiment 9.
By described LiAlO2-LiMnPO4/ C composite positive pole is made into lithium ion cell positive, tests its cycle performance and capacity, and test result is under 0.05C, and first discharge specific capacity is 117.3mAh/g, circulates 50 times, and capability retention is 79.6%.
Applicant states; the foregoing is only the specific embodiment of the present invention; but protection scope of the present invention is not limited thereto; person of ordinary skill in the field should understand; any belong to those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all drop within protection scope of the present invention and open scope.

Claims (10)

1. a composite positive pole, it is characterised in that, described composite positive pole comprises the carbon of lithium aluminate, lithium manganese phosphate and trace, and described lithium manganese phosphate load is on lithium aluminate surface, and the quality of described lithium aluminate accounts for the 0.1-10wt.% of lithium manganese phosphate quality; Described lithium aluminate to be size size the be hexagon sheet of 5-10 ��m, its crystalline phase is ��-LiAlO2; Column or the class of described lithium manganese phosphate to be granular size be 50-200nm are spherical.
2. the preparation method of composite positive pole according to claim 1, it is characterised in that, described method comprises the steps:
(1) phosphoric acid solution is dripped in lithium hydroxide solution, it is precipitated product; Precipitated product is washed, and vacuum-drying, calcining, obtains canescence phosphoric acid powder for lithium;
(2) manganous sulfate and Trilithium phosphate are joined in the mixed solution of polyoxyethylene glycol and water, obtain mixture;
(3) lithium aluminate of formula ratio is joined in mixture, move in reactor, carry out hydro-thermal reaction, obtain hydro-thermal reaction product, wherein, lithium aluminate to be size size the be hexagon sheet of 5-10 ��m, crystalline phase is �� crystalline phase;
(4) hydro-thermal reaction product is washed, dry, obtain the presoma of lithium aluminate compound phosphoric acid manganese lithium;
(5) presoma by lithium aluminate compound phosphoric acid manganese lithium carries out bag carbon process, calcines, obtain described composite positive pole at 500-700 DEG C.
3. preparation method according to claim 2, it is characterised in that, the concentration of step (1) described phosphoric acid solution is 0.5-3.0mol/L;
Preferably, the concentration of step (1) described lithium hydroxide is 1.0-3.0mol/L;
Preferably, step (1) described phosphoric acid solution drips in lithium hydroxide solution with the flow rate of 1.5-5mL/min;
Preferably, the temperature of step (1) described calcining is 150-300 DEG C, and the time of calcining is 2-5h;
Preferably, the ratio of the amount of substance of step (2) described manganous sulfate and Trilithium phosphate is (1.5-3.5): 1;
Preferably, the volume ratio of step (2) described polyoxyethylene glycol and water is (0.5-4): 2;
Preferably, step (2) described polyoxyethylene glycol is the combination of any one or at least two kinds in PEG400, PEG800 or PEG2000.
4. preparation method according to Claims 2 or 3, it is characterised in that, step (3) described lithium aluminate is with AAO template and Li2CO3For raw material prepares through hydrothermal method;
Preferably, the described lithium aluminate matrix of step (3) carries out vigorous stirring after joining in mixture;
Preferably, the temperature of step (3) described hydro-thermal reaction is 165-200 DEG C, and the time of hydro-thermal reaction is 6-24h;
Preferably, step (4) described drying is vacuum-drying;
Preferably, the described bag carbon of step (5) is treated to: mixed in dehydrated alcohol with carbon source by the presoma of lithium aluminate compound phosphoric acid manganese lithium, pulverizes, dry;
Preferably, described carbon source is the combination of any one or at least two kinds in xitix, glucose, sucrose, citric acid, oxyacetic acid, succsinic acid, PVA, ethylene glycol or polyoxyethylene glycol;
Preferably, the described presoma of lithium aluminate compound phosphoric acid manganese lithium is than 1:(0.15-0.35 with the mass ratio of carbon source);
Preferably, described pulverizing is: the presoma of lithium aluminate compound phosphoric acid manganese lithium is carried out ball milling, and the ball milling time is 2-6h;
Preferably, the temperature of described drying is 50-100 DEG C, and the dry time is 8-24h;
Preferably, described roasting carries out in an inert atmosphere, it is preferable to carry out in nitrogen atmosphere or argon gas atmosphere;
Preferably, the time of described calcining is 3-10h.
5. the preparation method of composite positive pole according to claim 1, it is characterised in that, described method comprises the steps:
(1) in the solution containing lithium source, manganese source and phosphorus source, add complexing agent, add the lithium aluminate of formula ratio afterwards, obtain mixing solutions, mixing solutions is made wet gel, wherein, lithium aluminate to be size size be six hexagon sheets of 5-10 ��m, crystalline phase is �� crystalline phase;
(2) by wet gel ageing, dry, obtain xerogel;
(3) by xerogel precalcining, carry out two calcinings afterwards, obtain described composite positive pole.
6. utilize the method described in claim 5, it is characterised in that, the mol ratio of Li, Mn and P in the described lithium source of step (1), manganese source and phosphorus source is (1-1.5): 1:1;
Preferably, the add-on of step (1) described complexing agent be in the molar weight of lithium in lithium source and manganese source manganese molar weight sum 1-3 doubly;
Preferably, step (1) described wet gel is by stirring mixing solutions at 70-90 DEG C of condition lower magnetic force, and evaporating solns obtains;
Preferably, step (1) described wet gel is sticky thick green colloidal sol;
Preferably, the described lithium source of step (1) is the combination of any one or at least two kinds in lithium hydroxide, Quilonum Retard or lithium acetate;
Preferably, the described manganese source of step (1) is manganous sulfate and/or manganous acetate;
Preferably, the described phosphorus source of step (1) is phosphoric acid and/or primary ammonium phosphate;
Preferably, step (1) described complexing agent is any one or two or more combination in citric acid, oxyacetic acid, succsinic acid, ethylene glycol or polyoxyethylene glycol;
Preferably, step (1) described water is deionized water;
Preferably, step (1) described lithium aluminate is with AAO template and Li2CO3For raw material prepares through hydrothermal method.
7. method according to claim 5 or 6, it is characterised in that, the temperature of the described wet gel ageing of step (2) is 10-35 DEG C;
Preferably, the time of the described wet gel ageing of step (2) is 10-24h;
Preferably, the temperature of step (2) described drying is 80-120 DEG C;
Preferably, the time of step (2) described drying is 5-15h.
8. according to the method one of claim 5-7 Suo Shu, it is characterised in that, also pulverize before the described xerogel precalcining of step (3);
Preferably, the temperature of step (3) described precalcining is 300-400 DEG C;
Preferably, the time of step (3) described precalcining is 2-5h;
Preferably, step (3) described precalcining carries out under inert atmosphere or reducing atmosphere;
Preferably, the mixed atmosphere of any one or at least two kind of step (3) described precalcining in nitrogen atmosphere, argon gas atmosphere or hydrogen atmosphere carries out.
9. according to the method one of claim 5-8 Suo Shu, it is characterised in that, the temperature of described two calcinings of step (3) is 500-650 DEG C;
Preferably, the time of described two calcinings of step (3) is 5-10h;
Preferably, the product after described two calcinings of step (3), through cooling, obtains described composite positive pole after pulverizing.
10. a lithium ion battery, it is characterised in that, described lithium ion battery comprises composite positive pole according to claim 1.
CN201610134832.1A 2016-03-09 2016-03-09 Composite cathode material and preparation method thereof and lithium-ion battery Pending CN105633402A (en)

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CN110224120A (en) * 2019-05-23 2019-09-10 清华大学深圳研究生院 Preparation method, combination electrode and the lithium ion battery of combination electrode
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CN108539146A (en) * 2018-03-15 2018-09-14 南京国轩电池有限公司 A kind of lithium ion battery composite cathode material and the preparation method and application thereof
CN110224120A (en) * 2019-05-23 2019-09-10 清华大学深圳研究生院 Preparation method, combination electrode and the lithium ion battery of combination electrode
CN113054157A (en) * 2021-03-15 2021-06-29 星恒电源股份有限公司 Double-composite modified spinel lithium manganate positive plate, preparation method thereof and lithium ion battery

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