WO2019043402A1 - Procédé de production de phosphate de fer lithié particulaire revêtu de carbone, phosphate de fer lithié revêtu de carbone et ses utilisations - Google Patents

Procédé de production de phosphate de fer lithié particulaire revêtu de carbone, phosphate de fer lithié revêtu de carbone et ses utilisations Download PDF

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Publication number
WO2019043402A1
WO2019043402A1 PCT/GB2018/052468 GB2018052468W WO2019043402A1 WO 2019043402 A1 WO2019043402 A1 WO 2019043402A1 GB 2018052468 W GB2018052468 W GB 2018052468W WO 2019043402 A1 WO2019043402 A1 WO 2019043402A1
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WO
WIPO (PCT)
Prior art keywords
iron phosphate
carbon
lithium iron
lithium
polyvinyl butyral
Prior art date
Application number
PCT/GB2018/052468
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English (en)
Inventor
Mark Copley
Maria Elena RIVAS-VELAZCO
Enrico Petrucco
Original Assignee
Johnson Matthey Public Limited Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Johnson Matthey Public Limited Company filed Critical Johnson Matthey Public Limited Company
Priority to CN201880051687.8A priority Critical patent/CN111132929A/zh
Priority to EP18766013.9A priority patent/EP3678989A1/fr
Publication of WO2019043402A1 publication Critical patent/WO2019043402A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/30—Alkali metal phosphates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • 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

Definitions

  • the present invention relates to lithium transition metal phosphate materials, their preparation and use as a cathode material in secondary lithium ion batteries.
  • Lithium metal phosphates with olivine structures have emerged as promising cathode materials in secondary lithium ion batteries.
  • Advantages of lithium metal phosphates compared with other lithium compounds include the fact that they are relatively benign environmentally, and have excellent safety properties during battery handling and operation.
  • lithium metal phosphates Relatively poor electrochemical performance of lithium metal phosphates has been attributed to their poor electronic conductivity, and their performance has been significantly improved by coating the particles with electronically conductive carbon. There remains a need for lithium metal phosphates which can be made by simple, cost effective and scalable processes, employ low cost precursors, and exhibit advantageous electrochemical properties such as increased capacity.
  • the present inventors have found that the electrochemical performance carbon-coated lithium iron phosphate can be improved by controlling the properties of the carbon-containing precursor used in its preparation.
  • the present inventors have found that it is particularly advantageous to use a polyvinyl butyral with particular properties.
  • polyvinyl butyrals are typically copolymers with the Formula I below:
  • the copolymer typically includes (e.g. consists of) vinyl alcohol residues (z), vinyl butyral residues (x) and optionally vinyl acetate residues (y).
  • the values of x, y and z in Formula I can be controlled to control the properties of the PVB.
  • the weight % of vinyl butyral residues (the residue of bracket x) is referred to as the butyryl content.
  • the weight % of vinyl alcohol residues (the residue of bracket z) is referred to as the hydroxyl content.
  • the weight % of vinyl acetate residues (the residue of bracket y) is referred to as the acetyl content.
  • the acetyl content may be the remainder after the hydroxyl content and butyryl content has been accounted for. Note that acetyl residues need not be present (i.e. the value of y may be zero). (The weight % of residues recited herein is intended to include the polymer backbone shown in Formula I.)
  • PVBs may be formed by reaction of a copolymer of polyvinyl alcohol and polyvinyl acetate with butyraldehyde, or by reaction of polyvinyl alcohol with butyraldehyde.
  • the present invention provides a process for producing particulate carbon-coated lithium iron phosphate, the process comprising:
  • a calcination step in which the product of the milling step is calcined to provide carbon coated particulate lithium iron phosphate
  • the carbon-containing precursor is polyvinyl butyral having a molecular weight distribution such that at least 75% of the polyvinyl butyral has a molecular weight in the range from 30000 to 90000.
  • the polyvinyl butyral may have a butyryl content of at least 70 wt%.
  • the polyvinyl butyral may have a hydroxyl content of 30 wt% or less.
  • the polyvinyl butyral may have a viscosity in the range from 50 to 350 cP when measured as a 10 wt% solution in isopropyl alcohol at a shear rate of 100 1/s.
  • present invention provides a process for producing particulate carbon-coated lithium iron phosphate, the process comprising:
  • a calcination step in which the product of the milling step is calcined to provide carbon coated particulate lithium iron phosphate
  • the carbon-containing precursor is polyvinyl butyral having a butyryl content of less than 84 wt% and a hydroxyl content of at least 16 wt%.
  • the polyvinyl butyral may have a viscosity in the range from 50 to 350 cP when measured as a 10 wt% solution in isopropyl alcohol at a shear rate of 100 1/s.
  • the polyvinyl butyral may have a molecular weight in the range from 30000 to 90000.
  • present invention provides a process for producing particulate carbon-coated lithium iron phosphate, the process comprising:
  • a calcination step in which the product of the milling step is calcined to provide carbon coated particulate lithium iron phosphate
  • the carbon-containing precursor is polyvinyl butyral having a viscosity in the range from 50 to 350 cP when measured as a 10 wt% solution in isopropyl alcohol at a shear rate of 100 1/s.
  • the polyvinyl butyral may have a butyryl content of at least 70 wt%.
  • the polyvinyl butyral may have a hydroxyl content of 30 wt% or less.
  • the polyvinyl butyral may have a molecular weight in the range from 30000 to 90000.
  • the present invention provides particulate carbon-coated lithium iron phosphate obtained or obtainable by a process described herein.
  • the present invention provides use of carbon-coated lithium iron phosphate of the present invention for the preparation of a cathode of a secondary lithium ion battery.
  • the present invention provides a cathode which comprises carbon-coated lithium iron phosphate of the present invention.
  • the present invention provides a secondary lithium ion battery, comprising a cathode which comprises carbon-coated lithium iron phosphate of the present invention.
  • the battery typically further comprises an anode and an electrolyte.
  • Figure 1 shows the results of electrochemical testing of the lithium iron phosphate samples prepared in Example 1 and Comparative Examples 1 and 2.
  • the present invention provides a process for making particulate carbon-coated lithium iron phosphate, using polyvinyl butyral as a carbon-containing precursor.
  • the PVB may have a molecular weight in the range from 30,000 to 90,000, e.g. from 40,000 to 80,000. Typically, the molecular weight distribution is such that at least 70%, at least 75%, at least 80%, at least 90% at least 95% or at least 99% (e.g. by number) of the PVB molecules have a molecular weight in the recited range.
  • the PVB may have a butyryl content in the range from 70 wt% to 95 wt%.
  • the butyryl content may be at least 70 wt%, at least 75 wt%, or at least 78 wt%.
  • the butyryl content may be 98 wt% or less, 95 wt% or less, 90wt% or less, 86 wt% or less, 85 wt% or less, 84 wt% or less, or 83 wt% or less.
  • the present inventors believe that a relatively high butyryl content is advantageous, particularly in combination with a relatively low molecular weight, since this results in carbon coated lithium iron phosphate with improved electrochemical properties.
  • the hydroxyl content of the PVB may be in the range from 5 wt% to 30 wt%.
  • the hydroxyl content may be at least at least 2 wt%, at least 5 wt%, at least 8 wt%, at least 10 wt%, at least 14 wt%, at least 15 wt%, at least 16 wt% or at least 17 wt%. It may be 30 wt% or less, 25 wt% or less or 22 wt% or less.
  • the present inventors believe that a relatively low hydroxyl content is advantageous, particularly in combination with a relatively low molecular weight, since this results in carbon coated lithium iron phosphate with improved
  • the butyryl content is the wt% of butyryl residues in the PVB polymer and the hydroxyl content is the wt% of hydroxyl residues in the PVB polymer.
  • the PVB may optionally include acetyl residues, and the content of the acetyl residues may be the balance of the content of the PVB. In other words, the sum of the acetyl content, the butyryl content and the hydroxyl content may be 100 wt%. Alternatively, where acetyl is not present, the sum of the butyryl content and the hydroxyl content may be 100 wt%.
  • the PVB may have a viscosity in the range from 50 to 350 cP when measured as a 10 wt% solution in isopropyl alcohol at a shear rate of 100 1/s. It may have a viscosity of at least 50 cP, at least 70 cP, at least 90 cP or at least 100 cP. It may have a viscosity of 350 cP or less, 300 cP or less, 250 cP or less 200 cP or less or 150cP or less. The present inventors have found that when the viscosity of the PVB is too high or too low, the capacity of the resulting carbon-coated lithium iron phosphate is reduced.
  • the particulate carbon-coated lithium iron phosphate of the present invention typically has the formula Li x Fe y P04, in which x is 0.8-1.2 and y is 0.8-1.2, and in which up to 10 atom % (e.g. up to 5 atom %) of the Fe may be replaced with a dopant metal, up to 10 atom % (e.g. up to 5 atom %) of the phosphate may be replaced with S0 4 and/or Si0 4 , and up to 10 atom % of the Li may be replaced with Na and/or K.
  • the lithium iron phosphate may have the formula LiFeP0 4 , in which up to 10 atom % (e.g.
  • the lithium iron phosphate may have the formula Li x Fe y P0 4 , in which x is 0.8-1.2 and y is 0.8-1.2.
  • the lithium iron phosphate may have the formula LiFeP0 4 .
  • the dopant metal may be one or more selected from Mn, Co, Ni, Al, Mg, Sn, Pb, Nb, B, Cu, Cr, Mo, Ru, V, Ga, Ca, Sr, Ba, Ti, Zr, Cd.
  • the dopant metal may be one or more selected from Mn, Al, Ti and Zr. It may be preferred that the lithium iron phosphate is undoped. Where the lithium iron phosphate is doped, typically dopant-containing precursor is added in the milling step.
  • the lithium iron phosphate may have a crystallite size of 90nm or less, e.g. 85nm or less, when determined by Rietveld analysis of XRD data.
  • the crystallite size may be at least 60nm or at least 70nm. Smaller observed crystallite sizes can indicate a shorter lithium diffusion distance within the particles, thereby enhancing electrochemical performance.
  • the carbon-coated lithium iron phosphate is typically prepared by a process comprising a milling step and a calcination step.
  • the milling step may be a dry milling step, or may be a wet milling step, e.g. carried out in the presence of a liquid, such as water or an organic solvent. Suitable organic solvents include isopropyl alcohol, glycol ether, acetone and ethanol.
  • the milling step may be a high energy milling step.
  • the term "high energy milling" is a term well understood by those skilled in the art, to distinguish from milling or grinding treatments where lower amounts of energy are delivered.
  • high energy milling may be understood to relate to milling treatments in which at least 100 kWh of energy is delivered during the milling treatment, per kilogram of solids being milled. For example, at least 150 kWh, or at least 200 kWh may be delivered per kilogram of solid being milled. There is no particular upper limit on the energy, but it may be less than 500 kWh, less than 400 kWh, or less than 350 kWh per kilogram of solids being milled. Energy in the range from 250 kWh/kg to 300 kWh/kg may be typical. The milling energy is typically sufficient to cause mechanochemical reaction of the solids being milled. In the milling step lithium-containing precursor, iron-containing precursor and
  • carbon-containing precursor are combined and subjected to milling. If phosphorus is not provided as part of one of the iron- or lithium- containing precursors added in the milling step, a separate phosphorous-containing precursor (e.g. phosphate-containing precursor) is typically added.
  • a separate phosphorous-containing precursor e.g. phosphate-containing precursor
  • the nature of the lithium- and carbon- containing precursors is not particularly limited in the present invention.
  • Suitable lithium-containing precursors include lithium carbonate (L12CO3), lithium hydrogen phosphate (LJ2HPO4) and lithium hydroxide (LiOH).
  • L12CO3 may be preferred.
  • Suitable iron-containing precursors include iron phosphate (FePCU) and iron oxalate. The iron phosphate may be hydrated (e.g. FePCU.xHaO) or may be dehydrated. FePCU may be preferred.
  • the iron-containing precursor and the lithium precursor (and optionally phosphorous-containing precursor and / or dopant-containing precursor) are combined in suitable proportions to give the desired stoichiometry to the lithium iron phosphate product.
  • the amount of PVB added is not particularly limited in the present invention.
  • the amount of carbon precursor may be selected to give a carbon content of 1 to 5 wt% in the carbon-coated lithium iron phosphate, e.g. 1 to 3 wt%.
  • the amount of carbon precursor added in the milling step may be in the range from 3 to 15 wt%, e.g. 3 to 7 wt%.
  • the product of the milling step is typically calcined under an inert atmosphere to provide the particulate carbon-coated lithium iron phosphate.
  • the calcination step performs two functions. Firstly, it results in pyrolysis or carbonisation of the carbon precursor to form a conductive carbon coating on the lithium iron phosphate particles.
  • the calcination is carried out in an inert atmosphere, for example in an inert gas such as argon or nitrogen. It may alternatively be carried out in a reducing atmosphere. It is typically carried out at a temperature in the range from 550°C to 800°C, e.g. from 600°C to 750°C, or from 600°C or 650°C to 700°C. 680°C is particularly suitable.
  • the calcination is carried out for a period of 3 to 24h. The calcination time depends on the scale of manufacture (i.e. where larger quantities are prepared, longer calcination times may be preferred.
  • the process of the present invention may further comprise the step of forming an electrode (typically a cathode) comprising the carbon-coated lithium iron phosphate.
  • an electrode typically a cathode
  • this is carried out by forming a slurry of the particulate carbon-coated lithium iron phosphate, applying the slurry to the surface of a current collector (e.g. an aluminium current collector), and optionally processing (e.g. calendaring) to increase the density of the electrode.
  • the slurry may comprise one or more of a solvent, a binder, additional carbon material and further additives.
  • the electrode of the present invention will have an electrode density of at least 2.3 g/cm 3 . It may have an electrode density of 2.8 g/cm 3 or less, or 2.65 g/cm 3 or less.
  • the electrode density is the electrode density (mass/volume) of the electrode, not including the current collector the electrode is formed on. It therefore includes contributions from the active material, any additives, and additional carbon material, and any binder used.
  • the lithium iron phosphate may be capable of being formed into an electrode having an electrode density as defined above when formed into an electrode, e.g. by the electrode formation method of the Examples.
  • the process of the present invention may further comprise constructing a battery or electrochemical cell including the electrode comprising the carbon-coated lithium iron phosphate.
  • the battery or cell typically further comprises an anode and an electrolyte.
  • the battery or cell may typically be a secondary (rechargeable) lithium ion battery.
  • LiFeP0 4 L12CO3, and hydrated FeP0 4 were mixed in the desired proportions to obtain stoichiometric LiFeP0 4 , along with PVB as carbon source (at 4.5wt%).
  • the precursors were subjected to roller ball milling for 24 hours, using 10mm YSZ media.
  • the samples were then calcined in argon at 680°C for 5 hours, to form olivine lithium iron phosphate coated with conductive carbon.
  • Three different PVBs were tested. Their properties are shown in Table 1 below. PVBs with the properties listed below are readily available from companies including Kurarat Europe GmbH, Sigma Aldrich, Eastman Chemical and Sekisui Japan.
  • the viscosity was determined in 10 wt% solutions in I PA at a shear rate of 100 1/s.
  • Table 2 below shows which PVBs were used to prepare the lithium iron phosphate of the Examples and the Comparative Examples.
  • the obtained lithium iron phosphate was formed into electrodes, using an electrode coating formulation.
  • the electrode coating formulation had a solids content of approximately 40% by weight.
  • the solids portion consisted of 90wt% of active material from the Examples, 5wt% carbon black (C65 from ImerysTM), 5 wt% binder (Solef 5130TM (polyvinylidene fluoride, 10wt% binder in n-methyl pyrrolidone).
  • the coating formulations were used to cast electrodes on a 20 ⁇ aluminium foil using a vacuum coater, to provide an electrode loading of 5 mg/cm 2 (the electrode loading refers to the mass of active material per area of electrode).
  • the coated electrodes were calendared to provide an electrode density of 2.0 g/cm 3 .
  • Electrochemical coin cells (2032 button cell from HohsenTM) were formed.
  • the electrolyte was LP30 from SolvonicTM, which is 1 M LiPF6 in 1 : 1 by weight mixture of dimethyl carbonate and ethylene carbonate.
  • the anode was 0.75mm thickness lithium, and the separator was a glass microfiber filter (WhatmanTM GF/F).
  • the pressure used to crimp the coin cell was 750 psi.
  • the lithium iron phosphate particles were subjected to XRD and the crystallite

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un procédé de production de phosphate de fer lithié particulaire revêtu de carbone, comprenant une étape de broyage et une étape de calcination. Le procédé met en œuvre du polyvinylbutyral présentant une distribution de poids moléculaire telle qu'au moins 75 % du polyvinylbutyral présente un poids moléculaire dans la plage de 30 000 à 90 000. Le procédé permet la formation de phosphate de fer lithié possédant des propriétés électrochimiques améliorées.
PCT/GB2018/052468 2017-09-04 2018-08-31 Procédé de production de phosphate de fer lithié particulaire revêtu de carbone, phosphate de fer lithié revêtu de carbone et ses utilisations WO2019043402A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201880051687.8A CN111132929A (zh) 2017-09-04 2018-08-31 用于制备颗粒状碳涂覆的磷酸铁锂的方法、碳涂覆的磷酸铁锂及其用途
EP18766013.9A EP3678989A1 (fr) 2017-09-04 2018-08-31 Procédé de production de phosphate de fer lithié particulaire revêtu de carbone, phosphate de fer lithié revêtu de carbone et ses utilisations

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GBGB1714100.3A GB201714100D0 (en) 2017-09-04 2017-09-04 Lithium metal phosphate, its preparation and use
GB1714100.3 2017-09-04

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WO2019043402A1 true WO2019043402A1 (fr) 2019-03-07

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EP (1) EP3678989A1 (fr)
CN (1) CN111132929A (fr)
GB (1) GB201714100D0 (fr)
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US20110114875A1 (en) * 2009-11-16 2011-05-19 Guiqing Huang Electrochemically active materials and precursors thereto
CN103427072A (zh) * 2012-05-16 2013-12-04 上海宝钢磁业有限公司 一种磷酸铁锂原位碳包覆方法
EP2883840A1 (fr) * 2013-07-09 2015-06-17 LG Chem, Ltd. Procédé pour préparer une nanopoudre de phosphate de métal lithium revêtu de carbone
CN104752692A (zh) * 2013-12-30 2015-07-01 北京有色金属研究总院 一种磷酸亚铁锂/碳复合正极材料的制备方法
CN105470530A (zh) * 2015-12-27 2016-04-06 同济大学 镍(ii)-1,1’-二茂铁二羧酸配合物电催化剂的制备方法

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EP2292557A1 (fr) * 2009-09-03 2011-03-09 Clariant International Ltd. Synthèse continue de lithium-fer-phosphate recouvert de carbone
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EP2883840A1 (fr) * 2013-07-09 2015-06-17 LG Chem, Ltd. Procédé pour préparer une nanopoudre de phosphate de métal lithium revêtu de carbone
CN104752692A (zh) * 2013-12-30 2015-07-01 北京有色金属研究总院 一种磷酸亚铁锂/碳复合正极材料的制备方法
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GB201714100D0 (en) 2017-10-18
EP3678989A1 (fr) 2020-07-15

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