CN104733729A - Industrialized reparation method of LiM1-xZxPO4/ C composite material - Google Patents

Industrialized reparation method of LiM1-xZxPO4/ C composite material Download PDF

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Publication number
CN104733729A
CN104733729A CN201410805739.XA CN201410805739A CN104733729A CN 104733729 A CN104733729 A CN 104733729A CN 201410805739 A CN201410805739 A CN 201410805739A CN 104733729 A CN104733729 A CN 104733729A
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preparation
lim
kinds
doping metals
compound
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郭庆山
秦尚伟
王强
马忠贺
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YINGKOU HANGSHENG SCIENCE & TECHNOLOGY INDUSTRY Co Ltd
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YINGKOU HANGSHENG SCIENCE & TECHNOLOGY INDUSTRY Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • 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 an industrialized preparation method of LiM1-xZxPO4/ C composite material, belonging to the technical field of new energy material preparation. The preparation method comprises the steps of dissolving lithium salt, a transition metal compound, a doping metal compound and phytic acid into deionized water according to the atom molar ratio of Li to M to Z to P in the general formula LiM1-xZxPO4, wherein transition metal M is at least one of iron, cobalt, manganese and nickel, the doping metal Z is at least one of V, Mg, Cr, Nb and Ti, and x is more than or equal to 0.0 and less than or equal to 0.2; after that, stirring the mixed solution, heating and drying; putting the dried product into an inert atmosphere protection furnace, carrying out heat treatment, and cooling to the room temperature to obtain the target product, namely, the LiM1-xZxPO4/C composite material. The method is wide in raw material source and simple in synthetic process; in the preparation process, the phytic acid can be taken as a phosphorus source, a metal chelating agent and a carbon source, so that the method is low in production cost; the prepared material is excellent in electrochemical performance and can be industrialized.

Description

A kind of LiM of industrialization 1-xz xpO 4the preparation method of/C composite
Technical field
The invention belongs to energy technical field of new material preparation, relate to a kind of preparation method preparing anode material for lithium-ion batteries, particularly a kind of employing and be easier to the liquid phase method technique of industrialization to prepare LiM 1-xz xpO 4the method of/C composite.
Background technology
Transition metal phosphate, such as olivine compounds LiMPO 4(wherein M is the one of Fe, Mn, Co, Ni, V), has very large importance for rechargeable battery.Their allow at about 3-5V to embedding reversible in lithium current potential/deviate from lithium ion, therefore can as the positive electrode of lithium ion battery.Owing to only changing a little at Lithium-ion embeding/deviate from period lattice parameter, such LiMPO 4repeatedly after discharge and recharge, structure can keep stable.In addition, after they are overcharged, also oxygen can not be discharged, this and LiCoO 2on the contrary, therefore can avoid with electrolyte reaction and on fire.
Phytic acid (IP6) is a common native compound, containing six carbon atom and six phosphates in its molecule.It is the original storage form of phosphorus in plant, the content in chaff and seed higher (in wheat bran and linseed about 3%).Phytic acid, as chelating agent, antioxidant, antistaling agent, water correction agent, fermentation accelerant, anticorrosive metal agent etc., is widely used in the industry fields such as food, medicine, paint, daily-use chemical industry, intermetallic composite coating, textile industry, plastics industry and Polymeric Industry.
The people such as Guo Zhiguo (a kind of phosphate/carbon composite material and preparation method thereof and application, 201110415557.8, in substantive examination) phosphate/carbon composite material of having selected phytic acid to prepare.But raw metal used in preparation process is more single, major part is sulfate and chlorate, is not but removed by the foreign ion such as sulfate radical and chloride ion, thus affect purity and the performance of material in follow-up processing procedure.And in part preparation process, selected the organic solution such as ethanol, ethylene glycol to make solvent, cause the increase of cost.Product need additionally add the carbon source such as polystyrene, polyvinyl alcohol, causes the complexity of technique and the increase of cost, and easily cause carbon coated or distribution uneven.
Olivine LiMPO 4inferior position be low-down electronics and ionic conductivity, this can affect performance and the high rate performance of its capacity.Usual way is that the contour conductive material of simple carbon coated can significantly improve LiMPO by its particle nanometer, doped metal ion or coated high connductivity material 4electronic conductivity, but not very large to the improvement result of the ionic conductivity of material; And doped metal ion can improve the ionic conductivity of material significantly, thus improve high rate performance.
Summary of the invention
The object of the present invention is to provide a kind of be easier to industrialization prepare anode material for lithium-ion batteries LiM 1-xz xpO 4the method of/C composite, in order to complete this object, the present invention adopts following technical scheme:
1) lithium salts, transistion metal compound, doping metals compound and phytic acid are pressed general formula LiM 1-xz xpO 4the atomic molar ratio of middle Li, M, Z, P is dissolved in (M is the transition metal in transistion metal compound, and Z is the doping metals in doping metals compound, and P is the phosphorus in phytic acid) in deionized water;
2) by step 1) mixed solution constantly stir, reaction 2-8h, be heated to subsequently 90-140 DEG C dry 2-16h;
3) by step 2) product of drying is placed in 600-750 DEG C, inert atmosphere protection stove sintering 6 ~ 12h, and be cooled to room temperature and obtain target product, be i.e. LiM 1-xz xpO 4/ C positive electrode material, wherein 0.0≤x≤0.2.
LiM is prepared in the present invention 1-xz xpO 4in process, the mol ratio of the lithium of interpolation, transition metal, doping metals, phosphorus is (0.8-1.2): (0.8-1): (0-0.2): (1.0-1.5).
In the present invention, described general formula LiM 1-xz xpO 4middle transition metal M is one or two or more kinds in iron, cobalt, manganese, nickel.
In the present invention, described general formula LiM 1-xz xpO 4middle doping metals Z is one or two or more kinds in V, Mg, Cr, Nb, Ti.
In the present invention, described transistion metal compound and doping metals compound are one or two or more kinds in chlorate, nitrate, sulfate, hydroxide and oxide.
In the present invention, when described transistion metal compound and doping metals compound are one or two or more kinds in chlorate, sulfate, ammoniacal liquor need be added regulate pH=6.0-7.5 in mixed solution, phytic acid-metal composite is precipitated, by filtration or centrifuge washing, sulfate radical or chloride ion is removed.
In the present invention, step 3) in inert atmosphere be one or two or more kinds in nitrogen, argon gas, argon gas/5% hydrogen.
In the present invention, in lithium phosphate/carbon composite material the content of carbon between 2.0-5.0%.
In the present invention, the reaction equation of phytic acid and metal and lithium salts is:
6M 2++C 6H 6(H 2PO 4) 6+6LiOH→C 6H 6(MPO 4) 6·6Li ++6H ++6H 2O
Reaction equation in heat treatment process is:
C 6H 6(MPO 4) 6·6Li +→6LiMP0 4+6C+6H +
The present invention adopts phytic acid to prepare LiM 1-xz xpO 4the method of/C composite has: 1) phosphate radical, metal are formed a fixed network by crosslinked action by phytic acid, thus ensures that lithium, metal, phosphorus, carbon fixation are in same molecule in follow-up dry heat processing procedure; 2) when the carbon in phytic acid and conductive agent or conductive agent predecessor also can prevent heat treatment while improving material conductivity, lithium phosphate particle grows up; 3) phytic acid is conventional water treatment agent, anticorrosive and food preservative, and raw material is easy to get and cheap.
The inventive method, except having the usual feature in above phosphorus source and carbon source, also has: the LiM 1) prepared compared with additive method 1-xz xpO 4in/C composite, carbon content is moderate, and need not additionally add other carbon sources or conductive material again, tap density is high, ensure that the high-energy-density of material, and the material prepared with conventional method carrys out ratio, and carbon distribution is more even, and chemical property is more excellent; 2) the present invention synthesizes the method for lithium phosphate/carbon composite material, formula is simple, material purity is higher, impurity is only the elements such as hydrocarbon oxygen, be easy in high-temperature process remove, and sulfate radical, chloride ion etc. that sintering process is not easily removed have been removed in preparation process, gained lithium phosphate/carbon composite material purity is higher, ensures the self-discharge rate that material is low.3) the raw metal wide material sources of the present invention's employing, synthesis technique is simple to operation, is easy to realize suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is LiFePO prepared by embodiment 1 4the X ray diffracting spectrum (XRD) of/C composite.
Fig. 2 is LiFePO prepared by embodiment 2 4/ C composite is the cyclic curve of button lithium ion battery in 1.0C multiplying power of positive electrode.
Fig. 3 is LiFe prepared by embodiment 4 0.98mg 0.02pO 4/ C composite is the first charge-discharge curve of button lithium ion battery in 0.1C multiplying power of positive electrode.
Fig. 4 is LiMn prepared by embodiment 5 0.7fe 0.3pO 4scanning electron microscopy (SEM) picture of/C composite.
Embodiment
Be described in detail the present invention below by specific embodiment, following embodiment is only for illustration of the present invention, but the practical range be not intended to limit the present invention.
Embodiment 1:
Adopt Fe (NO 3) 3preparation LiFePO 4/ carbon nano-composite material
13ml plant acid solution (0.167mol/L) is added in 10ml iron (III) nitrate solution (1mol/L), constantly stirs.After reaction 1h, 11mlLiOH solution (1mol/L) is joined in above-mentioned mixed solution, at 90 DEG C, stir evaporation.The viscous mass obtained thus is dried further at 140 DEG C.Dry complex ball grinder ball milling, powder 700 DEG C of heat treatment 10h under continuous print nitrogen atmosphere of acquisition.
Adopt the structure of X-ray diffraction analysis instrument to the material of preparation to analyze, acquired results shows, and prepared material is pure LiFePO4, and degree of crystallinity is better.
Embodiment 2:
Adopt FeCl 2preparation LiFePO 4/ carbon nano-composite material
13.5ml plant acid solution (0.167mol/L) is added in 10ml iron (II) chlorate (1mol/L), constantly stirs.After abundant reaction, by NH 4oH solution joins in above-mentioned mixed solution, and reaction 3h, makes Fe 2+phytic acid complex precipitates, and by complex, centrifugal or filtration, washes 2-3 time with pure water in filter process, generates to dripping liquor argenti nitratis ophthalmicus without white precipitate.Precipitation mix with 10ml LiOH solution (1mol/L), drying also as described in Example 1 mode heat-treat.
With the material of preparation for positive pole, with lithium sheet for negative pole, U.S. celgard2300 is barrier film, 1mol/LLiPF 6(DC:EC=1:1) as electrolyte, be assembled into the 1.0C discharge and recharge in 2.5-4.2V voltage range of CR2032 battery in glove box, circulate 200 times, capacity is substantially unattenuated, shows good cycle performance.
Embodiment 3:
Adopt FeSO 4preparation LiFePO 4/ carbon nano-composite material
Using the method for embodiment 2 to prepare, iron (II) sulfate liquor (1mol/L) single-candidate is replaced iron (II) chlorate, in filter process, washes 2-3 time with pure water, generating without white precipitate to dripping barium chloride solution.Precipitation mix with LiOH solution (1mol/L), drying also as described in Example 1 mode heat-treat.
Comparative example:
Use the method for embodiment 2 to prepare, iron (II) sulfate liquor (1mol/L) single-candidate is replaced iron (II) chlorate, adds phenmethylol as solvent, mix, at 220 DEG C, react 2h.React complete, be separated dry, obtain pulverulent solids, by this powder and glucose be in mass ratio 1:1 ground and mixed even after, 900 DEG C are carried out calcining 5h under an argon atmosphere, obtain lithium iron phosphate/carbon composite material.
Table 1 embodiment 3 and comparative example properties contrast
Result as can be seen from table 1, embodiments of the invention carbon content and sulfur content are all lower, thus make the tap density of material and self discharge conservation rate all than the height of comparative example, the high energy density of material that can make of tap density improves accordingly, and self-discharge rate is low thus ensure that fail safe and the cycle performance of battery.
Embodiment 4:
Adopt FeSO 4, MgSO 4preparation LiFe 0.98mg 0.02pO 4/ C nano composite material
The method of embodiment 2 is used to prepare, the single-candidate of iron (II) sulfate liquor (0.98mol/L) and magnesium (II) sulfate liquor (0.02mol/L) is replaced iron (II) chlorate, washing 2-3 time with pure water in filter process, generating without white precipitate to dripping barium chloride solution.Precipitation mix with LiOH solution (1mol/L), drying also as described in Example 1 mode heat-treat.
Embodiment 5:
LiMn 0.7fe 0.3pO 4the preparation of/carbon nano-composite material
Manganese (II) sulfate (0.7mol/L) and iron (II) sulfate, iron (II) chloride or iron (III) nitrate (0.3mol/L) are replaced iron (II) chlorate in embodiment 2, dried powder is 750 DEG C of heat treatment 8h under continuous print argon/5% hydrogen atmosphere.Prepared material granule is evenly distributed, and particle diameter is less, and primary particle size can reach hundreds of nanometer.

Claims (10)

1. the LiM of an industrialization 1-xz xpO 4the preparation method of/C composite, is characterized in that comprising the following steps:
1) be (0.8-1.2) by lithium salts, transistion metal compound, doping metals compound and phytic acid by the mol ratio of lithium, transition metal, doping metals, phosphorus: (0.8-1): (0-0.2): (1.0-1.5) is dissolved in deionized water;
2) by step 1) mixed solution constantly stir, make it fully react, be heated to 90-140 DEG C of oven dry subsequently;
3) by step 2) product of drying is placed in 600-750 DEG C, inert atmosphere protection stove sintering 6 ~ 12h, and be cooled to room temperature and obtain target product, be i.e. LiM 1-xz xpO 4/ C positive electrode material, wherein 0.0≤x≤0.2.
2. preparation method according to claim 1, is characterized in that: step 1) prepare LiM 1-xz xpO 4in process, by general formula LiM 1-xz xpO 4the atomic molar ratio of middle Li, M, Z, P is dissolved in deionized water; M is the transition metal in transistion metal compound, and Z is the doping metals in doping metals compound, and P is the phosphorus in phytic acid.
3. preparation method according to claim 1, is characterized in that: described general formula LiM 1-xz xpO 4middle transition metal M is one or two or more kinds in iron, cobalt, manganese, nickel.
4. the preparation method according to claim 1 or 3, is characterized in that: described transistion metal compound is one or two or more kinds in the chlorate of transition metal, nitrate, sulfate, hydroxide and oxide.
5. preparation method according to claim 1, is characterized in that: described general formula LiM 1-xz xpO 4middle doped metallic elements Z is one or two or more kinds in V, Mg, Cr, Nb, Ti.
6. preparation method according to claim 1 or 5, is characterized in that: described doping metals compound is one or two or more kinds in the chlorate of doping metals, nitrate, sulfate, hydroxide and oxide.
7. preparation method according to claim 1, it is characterized in that: when described transistion metal compound and doping metals compound are one or two or more kinds in chlorate, sulfate, ammoniacal liquor need be added regulate pH=6.0-7.5 in mixed solution, phytic acid-metal composite is precipitated, by filtration or centrifuge washing, sulfate radical or chloride ion is removed.
8. preparation method according to claim 1, is characterized in that: step 2) reaction time is 2-8h, drying time is 2-16h.
9. preparation method according to claim 1, is characterized in that: step 3) in inert atmosphere be one or two or more kinds in nitrogen, argon gas, argon gas/5% hydrogen.
10. preparation method according to claim 1, is characterized in that: positive electrode LiM 1-xz xpO 4the content of the middle carbon of/C is between 2.0-5.0%.
CN201410805739.XA 2014-12-19 2014-12-19 Industrialized reparation method of LiM1-xZxPO4/ C composite material Pending CN104733729A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106654239A (en) * 2017-03-01 2017-05-10 四川大学 Carbon-internally-doped lithium ion battery material and preparation method therefor
CN106784809A (en) * 2016-11-18 2017-05-31 山东精工电子科技有限公司 A kind of LiVOPO4/LiMPO4/ C composite material of core-shell structure and preparation method
CN110863266A (en) * 2019-11-01 2020-03-06 浙江大学 Metal phosphide nanofiber and preparation method thereof
CN115028216A (en) * 2022-08-12 2022-09-09 宜宾锂宝新材料有限公司 High-nickel ternary cathode material, preparation method thereof and lithium ion battery

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2098483A1 (en) * 2008-03-05 2009-09-09 High Power Lithium S.A. Synthesis of lithium metal phosphate/carbon nanocomposites with phytic acid
CN102437338A (en) * 2011-12-13 2012-05-02 中国科学院化学研究所 Phosphate/carbon composite material, and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2098483A1 (en) * 2008-03-05 2009-09-09 High Power Lithium S.A. Synthesis of lithium metal phosphate/carbon nanocomposites with phytic acid
CN102437338A (en) * 2011-12-13 2012-05-02 中国科学院化学研究所 Phosphate/carbon composite material, and preparation method and application thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106784809A (en) * 2016-11-18 2017-05-31 山东精工电子科技有限公司 A kind of LiVOPO4/LiMPO4/ C composite material of core-shell structure and preparation method
CN106784809B (en) * 2016-11-18 2019-07-05 山东精工电子科技有限公司 A kind of LiVOPO4/LiMPO4/ C composite material of core-shell structure and preparation method
CN106654239A (en) * 2017-03-01 2017-05-10 四川大学 Carbon-internally-doped lithium ion battery material and preparation method therefor
CN106654239B (en) * 2017-03-01 2019-09-24 四川大学 A kind of interior carbon dope lithium ion battery material and preparation method thereof
CN110863266A (en) * 2019-11-01 2020-03-06 浙江大学 Metal phosphide nanofiber and preparation method thereof
CN110863266B (en) * 2019-11-01 2021-04-20 浙江大学 Metal phosphide nanofiber and preparation method thereof
CN115028216A (en) * 2022-08-12 2022-09-09 宜宾锂宝新材料有限公司 High-nickel ternary cathode material, preparation method thereof and lithium ion battery
CN115028216B (en) * 2022-08-12 2022-10-28 宜宾锂宝新材料有限公司 High-nickel ternary cathode material, preparation method thereof and lithium ion battery

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Application publication date: 20150624