CN103474655B - A kind of preparation method of the potassium additive Mn iron phosphate compound anode material of lithium possessing high conductivity - Google Patents
A kind of preparation method of the potassium additive Mn iron phosphate compound anode material of lithium possessing high conductivity Download PDFInfo
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- CN103474655B CN103474655B CN201310289533.1A CN201310289533A CN103474655B CN 103474655 B CN103474655 B CN 103474655B CN 201310289533 A CN201310289533 A CN 201310289533A CN 103474655 B CN103474655 B CN 103474655B
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Abstract
The present invention relates to the preparation method of a kind of potassium additive Mn iron phosphate compound anode material of lithium possessing high conductivity, the chemical formula of this multielement-doped lithium iron phosphate is Li1‑xKxFe1‑yMnyPO4, wherein: x=0.15 0.3, y=0.3 0.35 the method comprise the steps: that (1) prepares nano-grade lithium iron phosphate presoma；(2) acetylene black is mixed with Polyethylene Glycol and ultrasonic disperse is in ethanol, form conductive carbon dispersion liquid；Described nano-grade lithium iron phosphate presoma is mixed with conductive carbon dispersion liquid, by compound ball milling in planetary ball mill；Material after ball milling is dried；Sinter under restitutive protection's atmosphere, prepare product.Lithium ion battery high conductivity potassium additive Mn iron phosphate compound anode material of lithium prepared by the present invention, adulterated by LiFePO4 K, Mn are modified to improve its Ionic diffusion energy and to suppress agglomeration, and form conductive carbon carbon network on its surface.
Description
Art
The present invention relates to the preparation method of a kind of potassium additive Mn iron phosphate compound anode material of lithium possessing high conductivity.
Background technology
Along with developing rapidly of battery industry, in order to solve the service life of battery, energy density, self discharge or quality etc.
Problems, occur in that various types of battery.At present, due to lithium battery have energy density height, length in service life,
The advantages such as light weight, self discharge are little, through becoming the first-selected electricity of the portable set such as communication apparatus, notebook computer
Source, and also begin to be applied in the equipment that electric motor car, national defence etc. are medium-and-large-sized.
LiFePO 4 material is the power lithium-ion battery positive electrode occurring and obtaining extensive commercial application in recent years.Its
Have and reversibly embed and the characteristic of removal lithium embedded.Compared with traditional lithium ion secondary battery anode material, its raw material
Source is more extensive, price is less expensive, avirulence, and non-environmental-pollution.LiFePO4 has high-energy-density (its theoretical ratio
Capacity is 170mAh/g, and product actual specific capacity can be more than 140mAh/g (0.2C, 25 DEG C)；Because it is without any to human body
Harmful heavy metal element, and become current safest anode material for lithium-ion batteries；The lattice stability of LiFePO4
Good, embedding and the abjection of lithium ion are little, so having good reversibility on the impact of lattice.
At present, the preparation method of lithium iron phosphate positive material mainly have high temperature solid-state method, liquid phase reactor method, sol-gal process and
Mechanical attrition method etc..High temperature solid-state method is at inert atmosphere protection by Li source compound, Fe source compound and P source compound
Lower roasting synthesizing iron lithium phosphate；The advantage of high temperature solid-state method is that technique simply, easily realizes industrialization, but reactant is the most mixed
Closing uneven, product grain, crystal grain are easily grown up, and purity is the highest, and primary particle is excessive causes lithium ion mobility path long,
Lithium ion conducting performance is poor, and therefore, chemical property is bad.
Summary of the invention
The present invention provides the preparation method of a kind of potassium additive Mn iron phosphate compound anode material of lithium possessing high conductivity, and using should
Positive electrode prepared by method, has excellent conductive performance and cyclical stability.
To achieve these goals, a kind of potassium additive Mn iron lithium phosphate compound anode material possessing high conductivity that the present invention provides
The preparation method of material, the chemical formula of this multielement-doped lithium iron phosphate is Li1-xKxFe1-yMnyPO4, wherein: x=0.15-0.3,
Y=0.3-0.35 the method comprises the steps:
(1) according to the mole of Li, K, Fe, Mn, P in above-mentioned chemical formula weigh Lithium hydrate, Ferrox.,
Ammonium dihydrogen phosphate, manganese acetate and potassium carbonate, mixing machinery resulting mixture one；
Mixture one is mixed and be dissolved in solvent with chelating agent mutually by the weight ratio of 1: 0.2-0.5, forms mixture two, wherein
Chelating agent is glucose sugar, and solvent is ethylene glycol；
By mixture two in planetary ball mill with rotating speed 400-500r/min ball milling 20-30h；
Mixture two after ball milling is placed in vacuum drier and is dried 12-18h the temperature of 100-150 DEG C and obtains powder, will
Gained powder disintegrating apparatus is pulverized；
Powder after pulverizing is placed in reducing atmosphere stove the Temperature pre-treatment 5-20h at 300-700 DEG C, obtains nanometer phosphoric acid
Ferrum lithium presoma；
(2) acetylene black and Polyethylene Glycol are mixed mutually by the weight ratio of 1: 1-2 and ultrasonic disperse is in ethanol, form conduction
Carbon dispersion liquid；
Described nano-grade lithium iron phosphate presoma and conductive carbon dispersion liquid are pressed nano-grade lithium iron phosphate presoma and conductive carbon weight ratio
10: 1-2 ratio mixing, by compound in planetary ball mill with rotating speed 400-500r/min ball milling 10-15h；
Material after ball milling is dried；
Sinter under restitutive protection's atmosphere, with 5-10 DEG C/min ramp, at temperature 750-800 DEG C Isothermal sinter
10-15h, lowers the temperature with 3-6 DEG C/min, prepares product.
Lithium ion battery high conductivity potassium additive Mn iron phosphate compound anode material of lithium prepared by the present invention, by LiFePO4
Doping K, Mn are modified to improve its Ionic diffusion energy and to suppress agglomeration, and form conductive carbon carbon net on its surface
Network so that it has good electric conductivity and cyclical stability.Therefore this composite is when for lithium ion battery,
There is charge-discharge velocity and longer service life faster.
Detailed description of the invention
Embodiment one
The chemical formula of this multielement-doped lithium iron phosphate is Li0.85K0.15Fe0.7Mn0.3PO4。
Lithium hydrate, Ferrox., di(2-ethylhexyl)phosphate is weighed according to the mole of Li, K, Fe, Mn, P in above-mentioned chemical formula
Hydrogen ammonium, manganese acetate and potassium carbonate, mixing machinery resulting mixture one；Mixture one and chelating agent are pressed the weight ratio of 1: 0.2
Mixing and be dissolved in solvent mutually, form mixture two, its complexing agent is glucose sugar, and solvent is ethylene glycol；By mixture two
With rotating speed 400r/min ball milling 30h in planetary ball mill；Mixture two after ball milling is placed in vacuum drier
The temperature of 100 DEG C is dried 8h and obtains powder, is pulverized by gained powder disintegrating apparatus；Powder after pulverizing is placed in reduction
At the Temperature pre-treatment 20h of 300 DEG C in atmosphere furnace, obtain nano-grade lithium iron phosphate presoma.
Acetylene black and Polyethylene Glycol are mixed mutually by the weight ratio of 1: 1 and ultrasonic disperse is in ethanol, form conductive carbon dispersion
Liquid；Described nano-grade lithium iron phosphate presoma and conductive carbon dispersion liquid are pressed nano-grade lithium iron phosphate presoma and conductive carbon weight ratio
10: 1 ratio mixing, by compound in planetary ball mill with rotating speed 400r/min ball milling 15h；By the thing after ball milling
Matter is dried；Sinter under restitutive protection's atmosphere, with 5 DEG C/min ramp, at 750 DEG C of Isothermal sinter 15h of temperature,
Lower the temperature with 3 DEG C/min, prepare product.
Embodiment two
The chemical formula of this multielement-doped lithium iron phosphate is Li0.7K0.3Fe0.65Mn0.35PO4。
Lithium hydrate, Ferrox., di(2-ethylhexyl)phosphate is weighed according to the mole of Li, K, Fe, Mn, P in above-mentioned chemical formula
Hydrogen ammonium, manganese acetate and potassium carbonate, mixing machinery resulting mixture one；Mixture one and chelating agent are pressed the weight ratio of 1: 0.5
Mixing and be dissolved in solvent mutually, form mixture two, its complexing agent is glucose sugar, and solvent is ethylene glycol；By mixture two
With rotating speed 500r/min ball milling 20h in planetary ball mill；Mixture two after ball milling is placed in vacuum drier
The temperature of 150 DEG C is dried 12h and obtains powder, is pulverized by gained powder disintegrating apparatus；Powder after pulverizing is placed in reduction
At the Temperature pre-treatment 5h of 700 DEG C in atmosphere furnace, obtain nano-grade lithium iron phosphate presoma.
Acetylene black and Polyethylene Glycol are mixed mutually by the weight ratio of 1: 2 and ultrasonic disperse is in ethanol, form conductive carbon dispersion
Liquid；Described nano-grade lithium iron phosphate presoma and conductive carbon dispersion liquid are pressed nano-grade lithium iron phosphate presoma and conductive carbon weight ratio
10: 2 ratio mixing, by compound in planetary ball mill with rotating speed 500r/min ball milling 10h；By the thing after ball milling
Matter is dried；Sinter under restitutive protection's atmosphere, with 10 DEG C/min ramp, at 800 DEG C of Isothermal sinter 10h of temperature,
Lower the temperature with 6 DEG C/min, prepare product.
Comparative example
By LiOH, FeSO4·7H2O、H3PO4Join in deionized water according to mol ratio 3: 1.1: 1.1, and add
The organic carbon source of one or more composition mixtures in sucrose, glucose, Polyethylene Glycol, polyvinyl alcohol or starch and mixing
Foreign material, described alloy is one or more in the compound of manganese, cobalt, vanadium, nickel, aluminum, magnesium, calcium, zinc etc.,
The content of alloy is 0.01%, is uniformly mixed.80 DEG C, in the closed reactor of 1MPa, mixing speed is
50r/min, reacts 9h, centrifuge dewatering, vacuum drying, is sintered under nitrogen protection, is warmed up to 5 DEG C/min
560 degree, Isothermal sinter 9h, then cool to room temperature with 2 DEG C/min, obtain the iron phosphate powder of carbon coated.
By above-described embodiment one, two and comparative example products therefrom and conductive black and binding agent Kynoar with mass ratio
The ratio mixing of 80: 10: 10, is compressed on nickel screen, is vacuum dried 24h at 150 DEG C, as working electrode.Reference electricity
Extremely lithium metal, electrolyte is 1mol/l LiPF6EC/DEC/DMC (volume ratio 1: 1: 1).It it is 25 DEG C in test temperature
Under carry out electric performance test, after tested this embodiment one with two material compared with the product of comparative example, first charge-discharge speed
Rate improves 30-35%, brings up to more than 1.5 times service life.
Claims (1)
1. possess a preparation method for the potassium additive Mn iron phosphate compound anode material of lithium of high conductivity, this multielement
The chemical formula of doped iron lithium phosphate is Li1-xKxFe1-yMnyPO4, wherein: 0.15≤x≤0.3,0.3 ＜ y≤0.35,
The method comprises the steps:
(1) according to the mole of Li, K, Fe, Mn, P in above-mentioned chemical formula weigh Lithium hydrate, Ferrox.,
Ammonium dihydrogen phosphate, manganese acetate and potassium carbonate, mechanical mixture resulting mixture one；
Mixture one is mixed and is dissolved in solvent with chelating agent mutually by the weight ratio of 1: 0.2-0.5, forms mixture two,
Its complexing agent is glucose sugar, and solvent is ethylene glycol；
By mixture two in planetary ball mill with rotating speed 400-500r/min ball milling 20-30h；
Mixture two after ball milling is placed in vacuum drier and is dried 12-18h the temperature of 100-150 DEG C and obtains powder
Material, pulverizes gained powder disintegrating apparatus；
Powder after pulverizing is placed in reducing atmosphere stove the Temperature pre-treatment 5-20h at 300-700 DEG C, obtains nanometer
Ferric lithium phosphate precursor；
(2) acetylene black and Polyethylene Glycol being mixed mutually by the weight ratio of 1: 1-2 and ultrasonic disperse is in ethanol, formation is led
Electrical carbon dispersion liquid；
Described nano-grade lithium iron phosphate presoma and conductive carbon dispersion liquid are pressed nano-grade lithium iron phosphate presoma and conductive carbon weight
Amount than 10: 1-2 ratio mixing, by compound in planetary ball mill with rotating speed 400-500r/min ball milling
10-15h；
Material after ball milling is dried；
Sinter under restitutive protection's atmosphere, with 5-10 DEG C/min ramp, at temperature 750-800 DEG C Isothermal sinter
10-15h, lowers the temperature with 3-6 DEG C/min, prepares product.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1684290A (en) * | 2004-04-13 | 2005-10-19 | 中国科学院物理研究所 | Positive pole material for secondary lithium cell and use |
| CN101630731A (en) * | 2009-07-27 | 2010-01-20 | 深圳市德方纳米科技有限公司 | Nanoscale lithium iron phosphate used as cathode material of lithium ion battery and preparation method thereof |
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| CN1684290A (en) * | 2004-04-13 | 2005-10-19 | 中国科学院物理研究所 | Positive pole material for secondary lithium cell and use |
| CN101630731A (en) * | 2009-07-27 | 2010-01-20 | 深圳市德方纳米科技有限公司 | Nanoscale lithium iron phosphate used as cathode material of lithium ion battery and preparation method thereof |
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Effective date of registration: 20160630 Address after: 061000, room 3, building 1201, Science Park, hi tech Industrial Development Zone, Hebei, Cangzhou, China Applicant after: Cangzhou Rising Chemicals Co., Ltd. Address before: Suzhou City, Jiangsu province 215100 Songjiang Road, Suzhou Industrial Park, No. 208 Building 8 Room 112 Applicant before: Suzhou Yiyuan Hongda Intellectual Property Agency Co., Ltd. |
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