WO2009003093A1 - Composés de phosphate de métal et batteries contenant ceux-ci - Google Patents

Composés de phosphate de métal et batteries contenant ceux-ci Download PDF

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WO2009003093A1
WO2009003093A1 PCT/US2008/068321 US2008068321W WO2009003093A1 WO 2009003093 A1 WO2009003093 A1 WO 2009003093A1 US 2008068321 W US2008068321 W US 2008068321W WO 2009003093 A1 WO2009003093 A1 WO 2009003093A1
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acid
precursor
lifepo
grams
lithium
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PCT/US2008/068321
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English (en)
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Jack Treger
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Tiax, Llc
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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
    • 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 invention relates to metal phosphate compounds and doped metal phosphate compounds that can be used as, for example, electrochemically active electrode materials in batteries, including lithium-ion batteries.
  • batteries can include electrodes containing an electrochemically active material having a crystallographic structure that allows reversible intercalation and de- intercalation of ions, such as lithium ions.
  • electrochemically active materials include LiCoO 2 , LiNiO 2 , LiC ⁇ i_ x Ni x O 2 and LiCoo.33Mno.33 Nio.33 ⁇ 2 , lithium metal phosphates (such as LiFePO 4 ), and lithium mixed metal phosphates.
  • LiFePO 4 for example, has been shown to have good energy capacity, low toxicity, outstanding cyclability, outstanding safety and low cost.
  • the invention features a method including combining a lithium source, a phosphorus source, and an iron source into an aqueous solution; forming LiFePO 4 from the solution, the LiFePO 4 having less than approximately 15% by weight of carbon; and forming an electrode comprising the LiFePO 4 .
  • the invention features a method, including forming a precursor comprising lithium, iron, phosphorus and an ammonium moiety; forming LiFePO 4 from the precursor; and forming an electrode comprising the LiFePO 4 .
  • Embodiments may include one or more of the following features.
  • the LiFePO 4 includes from approximately 1% by weight to approximately 15% by weight of carbon.
  • the LiFePO 4 has an average crystallite size of less than approximately 100 nm.
  • the LiFePO 4 has a DC electrical conductivity of equal to or greater than approximately I X lO "9 S/cm (IHz).
  • the lithium source includes a material selected from the group consisting of lithium hydroxide, lithium carbonate, lithium benzoate, and lithium acetate.
  • the phosphorus source includes a phosphorus-containing chelation agent, such as editronic acid or iminobis(methyl-phosphonic acid).
  • the iron source includes a material selected from the group consisting of iron oxide and iron carboxylate.
  • the iron source includes a material selected from the group consisting of ferric oxalate, ferric ammonium oxalate, ferrous oxalate, hydrated iron oxide, iron ammonium carboxylate, and ferric oxyhydroxide.
  • the method further includes combining in the aqueous solution an oxidizing agent capable of oxidizing the iron source, e.g., a ferrous iron source.
  • the oxidizing agent includes hydrogen peroxide or ozone.
  • the method further includes combining in the aqueous solution a carboxylic acid.
  • the method further includes combining in the aqueous solution a metal source different from the lithium source and the iron source.
  • the metal source includes niobium, zirconium, or titanium.
  • Forming the LiFePO 4 includes forming a precursor from the aqueous solution (e.g., by drying or heating the solution), and heating the precursor.
  • the aqueous solution is substantially free of a nitrate ion or a citrate ion.
  • the method further includes using the electrode to make a lithium ion battery.
  • Forming the LiFePO 4 is substantially free of mechanical mixing, such as milling to provide intimate mixing and particle size reduction.
  • Embodiments may include one or more of the following advantages.
  • LiFePO 4 can be produced with crystallites less than 100 nm (e.g., less than
  • reducing carbon content can be achieved by using a carboxylic acid anion that leaves less carbon in the LiFePO 4 product.
  • the method can be readily controlled to adjust the amount of carbon in the LiFePO 4 , as well as its electrical conductivity and crystallite size.
  • the LiFePO 4 can be substantially free of sulfur and/or a halide. All carbon contents provided herein are percentages by weight. As used herein, “substantially free” means less than approximately 5% by weight (e.g., less than approximately 3% by weight, or less than approximately 2% by weight).
  • An electrochemical cell can be a primary cell or a secondary cell.
  • Primary electrochemical cells are meant to be discharged, e.g., to exhaustion, only once, and then discarded. Primary cells are not intended to be recharged. Primary cells are described, for example, in David Linden, Handbook of Batteries (McGraw-Hill, 2d ed. 1995).
  • Secondary electrochemical cells can be recharged for many times, e.g., more than fifty times, more than a hundred times, or more. In some cases, secondary cells can include relatively robust separators, such as those having many layers and/or that are relatively thick. Secondary cells can also be designed to accommodate for changes, such as swelling, that can occur in the cells.
  • FIG. 1 is an illustration of an embodiment of a lithium-ion electrochemical cell.
  • FIG. 2 is a differential scanning calorimetry (DSC) scan of a precursor in
  • Comparative Example 1 dried at 100 0 C and pelletized at 14 tons/in 2 .
  • FIG. 3 is DSC scan of a precursor from an aqueous reaction OfLi 2 COs, etidronic acid and ferric ammonium oxalate.
  • FIG. 4 is a thermogravimetric analysis (TGA) scan of a precursor from an aqueous reaction of Li 2 CO 3 , etidronic acid and ferric ammonium oxalate.
  • TGA thermogravimetric analysis
  • FIG. 5 is a scanning electron microscope (SEM) photograph of Nb-doped LiFePO 4 prepared by a solution-chelation process.
  • FIG. 6 is an X-ray diffraction pattern of LiFePO 4 prepared in Example 1.
  • a lithium-ion electrochemical cell or battery 100 includes an anode 120 in electrical contact with a negative current collector 140, a cathode 160 in electrical contact with a positive current collector 180, a separator 200, and an electrolyte.
  • Anode 120, cathode 160, separator 200, and the electrolyte are contained within a case 220 to maintain charge balance. Examples of batteries 100 are described in U.S. Patent No. 7,025,907, or U.S. Patent No 5,910,382, hereby incorporated by reference.
  • Cathode 160 includes LiFePO 4 as an electrochemically active material that is capable of receiving and releasing lithium ions.
  • LiFePO 4 can sometimes have low intrinsic electrical conductivity and low intrinsic lithium ion diffusivity that can result in poor rate capability and power delivery.
  • the poor rate capability OfLiFePO 4 can be addressed by improving its electrical conductivity (such as by including carbon and/or metal doping) and improving its lithium ion diffusivity (such as by decreasing the primary crystallite size to less that 500 nm, for example, less than 100 nm, or less than 50 nm).
  • a chelation-solution processing method that uses low cost precursors, is safe, has high batch yields, does not require intensive mechanical precursor milling, does not require extensive capital equipment investment, and does not require strict process or pollution control.
  • This method combines elemental precursors at the molecular level without the need for high energy milling.
  • the method can produce a LiFePO 4 with less than approximately 15% by weight carbon (which can enhance the intrinsic gravimetric electrochemical capacity of an electrode containing the LiFePO 4 ) and good electrical conductivity.
  • the method includes forming a water soluble precursor containing lithium, phosphorus and iron by combining a lithium source (such as lithium hydroxide), a phosphorus source (such as etidronic acid) and an iron source (such as iron oxide (e.g., Fe 2 O 3 ) or ferric oxalate) in a solution, and then heating the precursor to form the LiFePO 4 .
  • a lithium source such as lithium hydroxide
  • a phosphorus source such as etidronic acid
  • an iron source such as iron oxide (e.g., Fe 2 O 3 ) or ferric oxalate)
  • the precursor can be prepared by first dissolving etidronic acid, or another phosphorus-containing chelation agent, in water.
  • the lithium source (such as LiOH or Li 2 CO 3 ) can then be added to produce a lithiated etidronic acid salt solution.
  • the iron source (such as ferric oxalate or ferric ammonium oxalate) can then be added to produce the precursor.
  • the added iron source can be solubilized by the lithiated etidronic acid solution to form a precursor complex containing Li, P and Fe that are mixed at the molecular level.
  • the iron source is in ferric form in order to create a soluble precursor, e.g., by using a ferric starting salt and/or oxidizing a ferrous salt in-situ.
  • LiFePO 4 formation and phase purity during calcination because the elements can travel a short distance (e.g., less than approximately 5 nm) for product formation, as compared to where the precursor elements are mechanically mixed, for example, by mechanically milling a lithium source (e.g., lithium carbonate), a phosphorus source (e.g., ammonium dihydrogen phosphate) and an iron source (e.g., ferrous oxalate) where the elements are separated by greater distances.
  • a lithium source e.g., lithium carbonate
  • a phosphorus source e.g., ammonium dihydrogen phosphate
  • iron source e.g., ferrous oxalate
  • the precursor is either a miscible mixture of a lithiated iron etidronic acid complex (such as Li 2 Fe2CH3C(OH)[PO(O)2]2(C2 ⁇ 4 )2 where etidronic acid, ferric oxalate and lithium hydroxide are the starting materials) and oxalic acid, or a single phase lithiated iron etidronic acid carboxylate complex (such as H 2 Li2Fe2CH 3 C(OH)[PO(O)2]2(C2 ⁇ 4)3). If the precursor is a mixture, then it appears to be miscible because, upon water removal, the mixture dries to a clear transparent glass with no phase apparent separation.
  • a lithiated iron etidronic acid complex such as Li 2 Fe2CH3C(OH)[PO(O)2]2(C2 ⁇ 4
  • a single phase lithiated iron etidronic acid carboxylate complex such as H 2 Li2Fe2CH
  • the precursor is a miscible mixture of the lithiated iron etidronic acid carboxylate complex (such as Li 2 Fe2CH 3 C(OH)[PO(O)2]2(C2 ⁇ 4)2) and (NFLt) 2 C 2 O 4 , or a single phase lithiated iron etidronic acid ammonium carboxylate complex (such as (NH 4 )6H 2 Li 2 Fe 2 CH3C(OH)[PO(O) 2 ] 2 (C 2 O 4 )6). If the precursor is a mixture, then it appears to be miscible because, upon water removal, the mixture dries to a clear transparent glass with no apparent phase separation.
  • the precursor is a mixture, then it appears to be miscible because, upon water removal, the mixture dries to a clear transparent glass with no apparent phase separation.
  • the concentration of the lithium source, phosphorus source, and iron source can each range from approximately 0.9 mol to approximately 1.1 mol.
  • the concentration of the lithium source can be greater than or equal to approximately 0.9 mol Li or approximately 1.0 mol Li; and/or less than or equal to approximately 1.1 mol Li or approximately 1.0 mol Li.
  • the concentration of the phosphorus source can be greater than or equal to approximately 0.9 mol P or approximately 1.0 mol P; and/or less than or equal to approximately 1.1 mol P or approximately 1.0 mol P.
  • the concentration of the iron source can be greater than or equal to approximately 0.9 mol Fe or approximately 1.0 mol Fe; and/or less than or equal to approximately 1.1 mol Fe or approximately 1.0 mol Fe.
  • the lithium source for preparing the precursor can contain only lithium, hydrogen, oxygen, nitrogen and carbon as elemental components to avoid contamination of the LiFePO 4 product with corrosive elements such as sulfur and halides.
  • Examples of lithium sources include lithium carbonate, lithium acetate, lithium benzoate and/or lithium hydroxide.
  • the moisture content of lithium carbonate, lithium benzoate and lithium acetate do not vary as much as lithium hydroxide thus their lithium assay is less sensitive to atmospheric humidity.
  • lithium hydroxide can absorb carbon dioxide if exposed to the atmosphere over time which additionally affects its lithium assay.
  • the phosphorus source can include a phosphorus-containing chelation agent , which can be an organic phosphonate, as described, for example, in CN1803590A, U.S.
  • LiFePO 4 examples include ferric oxalate (Fe 2 (C 2 O 4 )S) and ammonium ferric oxalate (Fe(NHZt) 3 (C 2 CU) 3 ).
  • ferric oxalate Fe 2 (C 2 O 4 )S
  • Fe(NHZt) 3 C 2 CU
  • the presence of ammonium in the precursor can lower the average crystallite size of the LiFePO 4 -C to less than 20 nm when calcined from 500 0 C to 600 0 C, or less than 15 nm when calcined from 500 0 C to 525 0 C.
  • the average crystallite size of the LiFePO 4 -C is greater than 20 nm when calcined at temperatures greater than 525 0 C.
  • the average LiFePO 4 -C crystallite size can be affected by the method of synthesis. As indicated above, decreasing the average LiFePO 4 -C crystallite size can increase the power capability OfLiFePO 4 -C cathodes by decreasing the average lithium ion diffusion length through the crystallite. Proposed reactions for precursor formation and calcination are shown below:
  • 2LiFePO 4 -C + 8CO + 3H 2 O (calcination) a. 2Fe(NH 4 )3(C 2 O 4 )3 + 2LiOH + CH 3 C(OH)[PO(OH) 2 ] 2 -> Li 2 Fe 2 CH 3 C(OH)[PO(O) 2 ] 2 (C 2 ⁇ 4) 2 + 3(NH 4 ) 2 C 2 O 4 + H 2 C 2 O 4 + 2H 2 O or (NH 4 ) 6 H 2 Li 2 Fe 2 CH 3 C(OH)[PO(O) 2 ] 2 (C 2 O 4 )6 + 2H 2 O
  • LiFePO 4 -C has a carbon content of less than approximately 15% by weight.
  • LiFePO 4 -C and LiFePO 4 refer to the same material, which contains carbon (e.g., less than approximately 15% by weight carbon).
  • ferric oxalate can be made in-situ by an aqueous oxidation of less costly ferrous oxalate using an oxidizing agent, such as hydrogen peroxide or ozone.
  • an oxidizing agent such as hydrogen peroxide or ozone.
  • a Li source such as lithium hydroxide or lithium carbonate
  • a phosphorus-containing chelation agent such as etidronic acid
  • a LiFePO 4 precursor can be produced as shown below: 2FeC 2 O 4 + 2LiOH + H 2 O 2 + CH 3 C(OH)[PO(OH) 2 ] 2 -> Li 2 Fe 2 CH 3 C(OH)[PO(O) 2 ] 2 (C 2 ⁇ 4) 2 + 4H 2 O
  • carboxylate anions can be used to produce a precursor, which the amount of carbon in the precursor, and thus the amount of carbon in LiFePO 4 to be adjusted.
  • a ferrous salt such as ferrous oxalate
  • an oxidizing agent such as hydrogen peroxide or ozone
  • a carboxylic acid other than citric acid
  • a lithium source such as lithium carbonate or lithium hydroxide and phosphorus containing chelation agent.
  • a mixed carboxylate precursor can form or a complete substitution of one carboxylate for another can be achieved, which can be described by the general equation (in all subsequent examples, the precursor is assumed to be a miscible mixture of a lithiated iron etidronic acid complex and a carboxylic acid and not a single phase lithiated iron etidronic acid carboxylate) :
  • One, two or more carboxylic acids can be used to produce a precursor containing one, two or more carboxylate anions.
  • An example is illustrated below in which the carboxylic acid is propionic acid and the iron source is ferrous oxalate.
  • a mixed carboxylate precursor containing both oxalate and propionate anion can be produced:
  • Carboxylic acids that produce a water soluble and homogenous precursor can be used.
  • carboxylic acids include but are not limited to aliphatic, aromatic and/or cyclical aliphatic acids. Additionally, the carboxylic acid group can be part of a molecule that contains other functional groups such as amines, amides, epoxides, furans, ketones, ethers, aldehydes, sugars, esters and/or unsaturated groups.
  • carboxylic acids such as butyric acid, glutaric acid, benzenetetracarboxylic acid, adipic acid, tartaric acid, pyruvic acid, and sarcosine can be used to produce a water soluble and homogenous precursor as well as LiFePO 4 .
  • ammonium carboxylates can be used.
  • ammonium carboxylates include ammonium propionate, ammonium oxalate, ammonium adipate, ammonium benzenetetracarboxylate, ammonium butyrate, ammonium glutarate and/or ammonium sarcosate.
  • ammonium carboxylate acid is ammonium propionate and the iron source is ferrous oxalate.
  • a mixed carboxylate precursor containing both oxalate and propionate anion can be produced:
  • the carboxylic acids are at least partially oxidized by hydrogen peroxide as judged by a darkening of the aqueous solution.
  • These partially oxidized acids can be used to produce a precursor, for example, as long as the oxidized carboxylic acid produces a water soluble and homogenous precursor.
  • Oxalic acid oxidizes to gaseous products, and therefore, excess oxalic acid may be used to maintain stoichiometry.
  • the oxalate moiety in ferrous oxalate may be oxidized by hydrogen peroxide, and as a result, can be replaced with excess oxalic acid or an oxalic acid salt such as ammonium oxalate.
  • a precursor is prepared using a hydrated iron oxide as the iron source.
  • An oxalic acid-buffered ammonium oxalate aqueous solution can solubilize hydrated iron oxide. The less crystalline hydrous ferric oxides are solubilized faster than the more crystalline oxides.
  • freshly prepared, poorly crystalline FeO(OH) may be converted into a precursor using ammonium oxalate as a complexing solublizer, as illustrated in the following reaction:
  • Ferric oxyhydroxide or ferrihydrite, FCsHOg ⁇ H 2 O is expected to be particularly soluble in an oxalic acid-buffered ammonium oxalate aqueous solution. Less crystalline two-line ferrihydrite is expected to more readily solubilize than the more crystalline six-line ferrihydrite.
  • Two-line and six-line refer to the number of X- ray diffraction peaks observed transposed over the amorphous diffraction pattern in the ferrihydrites.
  • Two-line ferrihydrite can be freshly prepared by precipitation from ferric nitrate at pH 7-8 using potassium hydroxide additions followed by washing.
  • a carbon source or a carbon monoxide source is used for carbothermal reduction of iron from ferric to ferrous during LiFePO 4 formation.
  • the carbon source needs to be present above 300 0 C (e.g., above 450 0 C) for carbothermal reduction.
  • the carbon source can also provide enhanced electrical conductivity to the LiFePO 4 if it is carbonized during calcination.
  • the carbon source can be from the carbon contained within the precursor molecule as well as added carbon that is not part of the precursor but is intimately mixed with the precursor by dissolving both the precursor and a carbon additive in water followed by drying. This mixing can occur during precursor formation.
  • carbon additives examples include glucose, oxalic acid, 2-furoic acid, adipic acid, benzenetetracarboxylic acid, propionic acid, glutaric acid and/or ascorbic acid.
  • additional carbon is used to form an electrically conductive LiFePO 4 product. It is believed that carbon can also help prevent crystallite size from increasing.
  • the aqueous precursor solution is dried at an elevated temperature to form a solid precursor in which the lithium, iron and phosphorus are mixed at the molecular level.
  • the drying temperature can be from approximately 80 to 150 0 C (e.g., approximately 100-130 0 C).
  • the upper drying temperature can be limited by the decomposition of the organic precursor in air which can begin to occur approximately 150 0 C. This decomposition can accelerate above 150 0 C, as judged by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) (FIG. 3 and FIG. 4).
  • the drying time can be from approximately 5 to 10 hrs (e.g., approximately 5 hrs at 130 0 C).
  • ferrous iron source such as ferrous oxalate
  • ferrous oxalate When a ferrous iron source is used, such as ferrous oxalate, it is oxidized in solution using an oxidizing agent (such as hydrogen peroxide), which can be an exothermic reaction that can increase the solution temperature and the hydrogen peroxide self-decomposition rate, leaving less available to oxidize the iron.
  • an oxidizing agent such as hydrogen peroxide
  • the solution can be kept cooler than 80 0 C (e.g., cooler than 60 0 C) during oxidation.
  • hydrogen peroxide can be added to account for both self-decomposition as well as hydrogen peroxide consumed due to oxidation of the carboxylic acid.
  • Carboxylic acid can also be oxidized and possibly consumed, so therefore excess carboxylic acid, or some other organic anion, can be added to maintain precursor stoichiometry
  • the dried precursor can milled to a powder and pelletized, e.g., at 6-18 tons/in 2 .
  • the milling is not meant to mix the iron, phosphorus and lithium since they are already mixed at the molecular level.
  • the milling serves to prepare the powder for pelletization.
  • Pelletization is not necessary to produce phase pure LiFePO 4 , however, it can prevent the powder from being blown around within the calcination furnace during vacuum and gas purging.
  • the precursor is ramped heated from room temperature up to a precursor decomposition temperature and then further up to a LiFePO 4 formation and crystallization temperature, under an inert atmosphere to prevent iron oxidation.
  • the precursor goes though three thermal stages: decomposition, LiFePO 4 formation and LiFePO 4 crystallization.
  • DSC data indicate that decomposition occurs between 150 and 250 0 C. LiFePO 4 formation and crystallization occur above 450 0 C (e.g., approximately 525 0 C) and accelerate with increasing temperature.
  • the precursor can be heated from room temperature up to approximately 200-300 0 C at a thermal ramp rate of 1-10 °C/min and held at 200-300 0 C for up to 2-5 hrs to decompose the precursor.
  • the precursor can be heated from 200-300 0 C to more than 450 0 C (the LiFePO 4 formation and crystallization temperature) at a ramp rate of 0.1 to 10 °C/min and held at more than 450 0 C for up to 48 hours.
  • the crystallization temperature and/or time are reduced (e.g., minimized) because they can cause crystallite growth, which can reduce lithium diffusivity and subsequent rate capability.
  • an additional calcination temperature consideration is formation of an electrically conductive phase including carbon (from carbonation of the organic precursor components) and/or an iron phosphide phase such as FeP, Fe 2 P and/or Fe 3 P (from carbothermal reduction of c- LiFePO 4 and/or presence of metallic dopants).
  • Carbonation of the organic component OfLiFePO 4 and formation of iron phosphide phases are strongly affected by calcination temperature and to a lesser degree by calcination time.
  • An acceptable electrical conductivity can be produced at a calcination temperature above 525 0 C (e.g., above approximately 600 0 C or above approximately 650 0 C).
  • the precursor pellet undergoes expansion and can foam up during calcination due the release of volatile gases.
  • the LiFePO 4 produced in such a case has comparable physical properties to LiFePO 4 produced by precursor pellets that do not expand during calcination (e.g., they have high crystallographic phase purity and have crystallite size below 100 nm.) FIG.
  • the formed LiFePO 4 can have low crystallite size, low carbon content, and/or good electrical conductivity.
  • the crystallite size ranges from approximately 10 nm to approximately 500 nm.
  • the crystallite size can be greater than or equal to approximately 10 nm, approximately 50 nm, approximately 75 nm, approximately 100 nm, approximately 200 nm, approximately 300 nm, or approximately 400 nm; and/or less than or equal to approximately 500 nm, approximately 400 nm, approximately 300 nm, approximately 200 nm, approximately 100 nm, approximately 75 nm, or approximately 50 nm.
  • the carbon content ranges from approximately 0% to approximately 15%.
  • the carbon content can be greater than or equal to approximately 0%, approximately 3%, approximately 5%, approximately 7%, approximately 9%, approximately 11%, or approximately 13%; and/or less than or equal to approximately 15%, approximately 14%, approximately 12%, approximately 10%, approximately 8%, approximately 6%, approximately 4%, or approximately 2%.
  • the electrical conductivity ranges from approximately 5X10 "11 S/cm (IHz) to approximately IXlO "3 S/cm (IHz).
  • the electrical conductivity can be greater than or equal to approximately 5X10 "11 S/cm (IHz), approximately IXlO "9 S/cm (IHz), approximately IXlO "8 S/cm (IHz), or approximately IXlO "5 S/cm (IHz); and/or less than or equal to approximately IXlO "3 S/cm (IHz), approximately IXlO "5 S/cm (IHz), approximately IXlO "8 S/cm (IHz), approximately IXlO "9 S/cm (IHz), or approximately 5X10 "11 S/cm (IHz).
  • One or more metallic dopants can be included in cathode 160 to enhance the electrical conductivity and the rate capability OfLiFePO 4 .
  • the processes described herein can include incorporation of metallic dopant(s) and dispersal of the dopant(s) at the molecular level without the need for intensive mechanical mixing or grinding since the materials are mutually soluble.
  • the metallic dopant(s) can be dissolved along with the lithium, iron and the phosphorus-containing chelation agent in water.
  • aqueous soluble metallic dopants examples include, ammonium zirconium carbonate, ammonium vanadate, titanium(IV)bis (ammonium lactato)dihydroxide and ammonium niobate(V)oxalate hydrate.
  • concentration of the metallic dopant(s) can range from approximately 0.0005 mol M per mole Li to approximately 0.05 mol M per mole Li where M is a metal such as Nb, Zr and Ti.
  • the concentration of the metallic dopant(s) can be greater than or equal to approximately 0.0005 mole M per mole Li , approximately 0.005 mole M per mole Li, or approximately 0.01 mole M per mole Li; and/or less than or equal to approximately 0.05 mole M per mole Li , approximately 0.02 mole M per mole Li, or approximately 0.01 mole per mole Li.
  • Cathode 160 can further include a binder to enhance the structural integrity of the cathode.
  • binders include polymers and co-polymer, such as polyethylene, polyacrylamides, styrenic block co-polymers (e.g., KratonTM G), Viton®, and various fluorocarbon resins, including polyvinylidene fluoride (PVDF), polyvinylidene fluoride co-hexafluoropropylene (PVDF-HFP), and polytetrafluoroethylene (PTFE).
  • PVDF polyvinylidene fluoride
  • PVDF-HFP polyvinylidene fluoride co-hexafluoropropylene
  • PTFE polytetrafluoroethylene
  • anode 120 can include any material capable of reversibly receiving lithium ions during the charging process and reversibly releasing (e.g., by insertion/de -insertion or intercalation/deintercalation) these ions during the discharging process of a lithium ion battery.
  • materials that can be included in anode 120 are graphites, carbons, Li 4 TIsOi 2 , tin alloys, silica alloys, intermetallic compounds, lithium metal, lithium alloys, and mixtures of any two or more thereof.
  • Separator 200 can include any material capable of providing electrical isolation between cathode 160 and anode 120, while allowing ions to pass through the separator.
  • materials that can be included in separator 200 include microporous single layer of polyethylene (PE), microporous single layer of polypropylene (PP), microporous PP/PE/PP tri-layer separator, and polyolefm/inorganic hybrid microporous separator.
  • the electrolyte may be a solid or liquid non-aqueous electrolyte.
  • solid electrolytes include polymeric electrolytes such as lithium salt complexes of polyethylene oxide, or dimensionally stable lithium salt solutions of gelled polymers such as polyphosphazene, and combinations thereof.
  • liquid electrolyte solvents include ethylene carbonate, diethylene carbonate, propylene carbonate, and combinations thereof.
  • the electrolyte can be provided with a lithium electrolyte salt. Examples of salts include LiPF 6 , LiBF 4 , and LiClO 4 .
  • DC electrical conductivity was determined by mixing approximately 100 mg of sample with 5 mg of Dupont TeflonTM 6C powder in a mortar until a sheet was created.
  • the sheet was ground into a powder using a small WaringTM- type blender.
  • the powder was then reformed into a sheet using a mortar.
  • the sheet was reground into a powder using a small WaringTM- type blender.
  • the powder was pressed into a 1.5 cm diameter by about 0.2-0.3 mm thick pellet using a 1.5 cm die set and a pressure of 9 tons.
  • the pellet was mounted between two 1.5 cm diameter gold-plated steel disks and 2,000 Ib of feree was applied to the disks.
  • the DC electrical resistance was measured at IHz using a EG&G Princeton Applied Research Model 273 A potentiostat/galvanostat controlled by ZplotTM software. Carbon content was measured by a combustion technique at Galbraith Laboratories using ASTM-D5393.
  • Powder X-ray diffraction patterns were collected in continuous scans between 5 and 120 degrees in 2-theta using an automated Shimadzu XRD-6000 diffractometer.
  • the X-ray diffraction patterns were structurally analyzed using the Rietveld technique with JadeTM software, available from Materials Data Inc. Crystallite size was determined using the Scherrer equation.
  • Example 1 Ferric ammonium oxalate iron source and etidronic acid phosphorus source
  • etidronic acid solution (59% etidronic acid) was diluted with 50 ml of water. 1.64 grams of lithium carbonate was slowly added with stirring. After effervescence ceased, 150 ml of water was added. 16.85 grams of ferric ammonium oxalate was dissolved into the solution. All dissolutions were performed at room temperature. After dissolution, the solution was poured into a Pyrex dish and dried at 130 0 C for 10 hrs. After drying, the precursor was scraped from the dish into a mortar and briefly ground into a powder. 4 grams of precursor powder was pelletized at 16 tons/in 2 in a 1-inch diameter die.
  • the pelletized precursor was then placed in a copper foil covered ceramic boat, and the boat was placed in a 1.5-in diameter tube furnace.
  • the tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon.
  • Argon gas was then purged at a constant 80 cc/min.
  • the furnace was heated from room temperature to 200 0 C at 5°C/min, held at 200 0 C for 2 hrs, ramped to 500 0 C at 2 °C/min, held at 500 0 C for 5 hrs, ramped to 700 0 C at 2 °C/min, and held at 700 0 C for 10 hrs.
  • the Scherrer derived crystallite size is 53 nm and the carbon content is 9% (by combustion).
  • the DC electrical conductivity is 8.5 X 10 "5 S/cm (lHz).
  • Example 2 Ferric oxalate iron source and iminobisfmethyl-phosphonic acid) phosphorus source
  • the tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon. Argon gas was then purged at a constant 80 cc/min. The furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 500 0 C at 2 °C/min, held at 500 0 C for 5 hrs, ramped to 700 0 C at 2 °C/min and held at 700 0 C for 10 hrs.
  • the Scherrer derived crystallite size is 58 nm and the carbon content is 5.5% (by combustion).
  • the DC electrical conductivity is 5 X 10 "6 S/cm (lHz).
  • Example 3 Ferric ammonium oxalate iron source and iminobisfmethyl-phosphonic acid) phosphorus source
  • the tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon. Argon gas was then purged at a constant 80 cc/min. The furnace was heated from room temperature to 200 0 C at 5 °C/min , held at 200 0 C for 2 hrs, ramped to 500 0 C at 2 °C/min, held at 500 0 C for 5 hrs, ramped to 700 0 C at 2 °C/min, and held at 700 0 C for 10 hrs.
  • V 290.4139718 (all in angstroms).
  • the Scherrer derived crystallite size is 26 nm and the carbon content is 7.9% (by combustion).
  • the DC electrical conductivity is 3 X 10 "6 S/cm (lHz).
  • Example 4 Ferrous oxalate iron source and etidronic acid phosphorus source, 0.5 mole oxalic acid/mole Fe carbon additive
  • the precursor was scraped from the dish into a mortar and briefly ground into a powder. 4 grams of precursor powder was pelletized at 16 tons/in 2 in a 1-inch diameter die. The pelletized precursor was then placed in a copper foil covered ceramic boat, and the boat placed in a 1.5-inch diameter tube furnace. The tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon. Argon gas was then purged at a constant 80 cc/min.
  • the furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 500 0 C at 2 °C/min, held at 500 0 C for 5 hrs, ramped to 700 0 C at 2 °C/min, held at 700 0 C for 10 hrs.
  • the Scherrer derived crystallite size is 27 nm and the carbon content is 6.9% (by combustion).
  • the DC electrical conductivity is 1.9 X 10 "6 S/cm (lHz).
  • Example 5 Ferrous oxalate iron source and etidronic acid phosphorus source, l.Omole oxalic acid/mole Fe carbon additive
  • the Scherrer derived crystallite size is 27 nm and the carbon content is 6.9% (by combustion).
  • the DC electrical conductivity is 1.9 X 10 "6 S/cm (lHz).
  • Example 6 Ferrous oxalate iron source and iminobisfmethyl-phosphonic acid) phosphorus source 0.5 mole oxalic acid/mole Fe carbon additive
  • the Scherrer derived crystallite size is 38 nm and the carbon content is 5% (by combustion).
  • the DC electrical conductivity is 4 X 10 "8 S/cm (IHz).
  • Example 7 Mixed carboxylate precursor using 1.0 mole propionic acid /mole Fe 7.72 grams of Etidronic acid solution (59% etidronic acid) and was diluted with 50 ml of water. 3.29 grams of propionic acid was next added and dissolved. 1.64 grams of lithium carbonate was slowly added with stirring. After effervescence ceased, 150 ml of water was added. 7.99 grams of ferrous oxalate was added.
  • Argon gas was then purged at a constant 80 cc/min.
  • the furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 500 0 C at 2 °C/min, held at 500 0 C for 5 hrs, ramped to 700 0 C at 2 °C/min, and held at 700 0 C for 10 hrs.
  • the Scherrer derived crystallite size is 29 nm and the carbon content is 8% (by combustion).
  • the DC electrical conductivity is 5.4 X 10 "6 S/cm (lHz).
  • Example 8 Mixed carboxylate precursor using 1.0 mole butyric acid /mole Fe
  • V 290.9637303 (all in angstroms).
  • the Scherrer derived crystallite size is 33 nm and the carbon content is 7.8% (by combustion).
  • the DC electrical conductivity is 7 X 10 "9 S/cm (lHz).
  • Example 9 Mixed carboxylate precursor using 1.0 mole glutaric acid /mole Fe
  • Etidronic acid solution (59% etidronic acid) was diluted with 50 ml of water. 5.86 grams of glutaric acid was next added and dissolved. 1.64 grams of lithium carbonate was slowly added with stirring. After effervescence ceased, 150 ml of water was added. 7.99 grams of ferrous oxalate was added. Stirring was maintained at all times. Finally, 7 grams of 50% H 2 O 2 was slowly added. Heat was generated so the solution was kept between 30 0 C and 50 0 C with a water bath. After dissolution, the solution was poured into a Pyrex dish and dried at 130 0 C for 10 hrs. After drying, the precursor was scraped from the dish into a mortar and briefly ground into a powder.
  • the Scherrer derived crystallite size is 28 nm and the carbon content is 13% (by combustion).
  • the DC electrical conductivity is 6 X 10 " 5 S/cm (IHz).
  • the solution was poured into a Pyrex dish and dried at 130 0 C for 10 hrs. After drying, the precursor was scraped from the dish into a mortar and briefly ground into a powder. 4 grams of precursor powder was pelletized at 16 tons/in 2 in a 1-inch diameter die. The pelletized precursor was then placed in a copper foil covered ceramic boat, and the boat placed in a 1.5-inch diameter tube furnace. The tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon. Argon gas was then purged at a constant 80 cc/min.
  • the furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 500 0 C at 2 °C/min, held at 500 0 C for 5 hrs, ramped to 700 0 C at 2 °C/min, and held at 700 0 C for 10 hrs.
  • the Scherrer derived crystallite size is 34 nm and the carbon content is 8.9% (by combustion).
  • the DC electrical conductivity is 1.9 X 10 "5 S/cm (lHz).
  • Example 11 Mixed carboxylate precursor using 1.0 mole 2-furoic acid /mole Fe
  • the Scherrer derived crystallite size is 46 nm and the carbon content is 17.4% (by combustion).
  • the DC electrical conductivity is 4.2 X 10 "5 S/cm (IHz).
  • Example 12 Mixed carboxylate precursor using l.Omole adipic acid /mole Fe 7.72 grams of etidronic acid solution (59% etidronic acid) and was diluted with 50 ml of water. 6.5 grams of adipic acid was next added and dissolved. 1.64 grams of lithium carbonate was slowly added with stirring. After effervescence ceased, 150 ml of water was added. 7.99 grams of ferrous oxalate was added. Stirring was maintained at all times. 7 grams of 50% H 2 O 2 was slowly added. Heat was generated so the solution was kept between 30 0 C and 50 0 C with a water bath.
  • the solution was poured into a Pyrex dish and dried at 130 0 C for 10 hrs. After drying, the precursor was scraped from the dish into a mortar and briefly ground into a powder. 4 grams of precursor powder was pelletized at 16 tons/in 2 in a 1-inch diameter die. The pelletized precursor was then placed in a copper foil covered ceramic boat, and the boat placed in a 1.5-inch diameter tube furnace. The tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon. Argon gas was then purged at a constant 80 cc/min.
  • the furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 500 0 C at 2 °C/min, held at 500 0 C for 5 hrs, ramped to 700 0 C at 2 °C/min, and held at 700 0 C for 10 hrs.
  • V 290.4913311 (all in angstroms).
  • the Scherrer derived crystallite size is 48 nm and the carbon content is 14.6% (by combustion).
  • the DC electrical conductivity is 5.2 X 10 "4 S/cm (lHz).
  • Example 13 Mixed carboxylate precursor using 1.0 mole tartaric acid /mole Fe
  • the Scherrer derived crystallite size is 86 nm and the carbon content is 1.6% (by combustion).
  • the DC electrical conductivity was 3.6 X 10 "9 S/cm (IHz).
  • Example 14 - Mixed carboxylate precursor using 1.0 mole pyruvic acid /mole Fe
  • precursor powder 4 grams was pelletized at 16 tons/in2 in a 1-inch diameter die. The pelletized precursor was then placed in a copper foil covered ceramic boat, and the boat placed in a 1.5-inch diameter tube furnace. The tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon. Argon gas was then purged at a constant 80 cc/min. The furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 500 0 C at 2 °C/min, held at 500 0 C for 5 hrs, ramped to 700 0 C at 2 °C/min, and held at 700 0 C for 10 hrs.
  • the Scherrer derived crystallite size is 78 nm and the carbon content is 1.5% (by combustion).
  • the DC electrical conductivity is 1.1 X 10 "7 S/cm (IHz).
  • Example 15 Mixed carboxylate precursor using 1.0 mole sarcosine /mole Fe
  • the Scherrer derived crystallite size is 47 nm and the carbon content is 4.2% (by combustion).
  • the DC electrical conductivity is 1 X 10 "7 S/cm (IHz).
  • Example 16 Mixed carboxylate precursor using 0.4 mole 2-furoic acid /mole Fe and 0.5mole ammonium oxalate/mole Fe
  • the precursor was scraped from the dish into a mortar and briefly ground into a powder. 4 grams of precursor powder was pelletized at 16 tons/in 2 in a 1-inch diameter die. The pelletized precursor was then placed in a copper foil covered ceramic boat, and the boat placed in a 1.5-inch diameter tube furnace. The tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon. Argon gas was then purged at a constant 80 cc/min.
  • the furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 500 0 C at 2 °C/min, held at 500 0 C for 5 hrs, ramped to 700 0 C at 2 °C/min, and held at 700 0 C for 10 hrs.
  • the Scherrer derived crystallite size is 47nm and the carbon content is 6% (by combustion).
  • the DC electrical conductivity is 2 XlO "5 S/cm (IHz).
  • Example 17 Mixed carboxylate precursor using 1.0 mole benzenetetracarboxylic acid /mole Fe calcined at 525 0 C
  • the solution was poured into a Pyrex dish and dried at 130 0 C for 10 hrs. After drying, the precursor was scraped from the dish into a mortar and briefly ground into a powder. 4 grams of precursor powder was pelletized at 16 tons/in 2 in a 1-inch diameter die. The pelletized precursor was then placed in a copper foil covered ceramic boat, and the boat placed in a 1.5-inch diameter tube furnace. The tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon. Argon gas was then purged at a constant 80 cc/min.
  • the furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 525°C at 2 °C/min, and held at 525°C for 15 hrs.
  • the Scherrer derived crystallite size is 32 nm and the carbon content is 8% (by combustion).
  • the DC electrical conductivity is 1.8 X 10 "10 S/cm (IHz).
  • Example 18 - Mixed carboxylate precursor using 1.0 mole adipic acid /mole Fe calcined at 525°C
  • precursor powder 4 grams was pelletized at 16 tons/in 2 in a 1-inch diameter die. The pelletized precursor was then placed in a copper foil covered ceramic boat, and the boat placed in a 1.5-inch diameter tube furnace. The tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon. Argon gas was then purged at a constant 80 cc/min. The furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 525 0 C at 2 °C/min, and held at 525 0 C for 15 hrs.
  • the Scherrer derived crystallite size is 18 nm and the carbon content is 14.5% % (by combustion).
  • the DC electrical conductivity is 3.8 X 10 "10 S/cm (lHz).
  • Example 19 Ferrous oxalate iron source and etidronic acid phosphorus source (no excess carbon source)
  • the Scherrer derived crystallite size is 206 nm and the carbon content is ⁇ 0.5% (by combustion).
  • the DC electrical conductivity is 3.4 X 10 "9 S/cm (IHz).
  • Example 20 Ferric ammonium oxalate iron source and 1 mole % Nb doping
  • etidronic acid solution (59% etidronic acid) was diluted with 50 ml of water. 1.64 grams of lithium carbonate was slowly added with stirring. After effervescence ceased, 150 ml of water was added. 16.85 grams of ferric ammonium oxalate and 0.2 grams of ammonium niobate(V)oxalate hydrate was dissolved in the solution. All dissolutions were performed at room temperature. After dissolution, the solution was poured into a Pyrex dish and dried at 130 0 C for 10 hrs. After drying, the precursor was scraped from the dish into a mortar and briefly ground into a powder. 4 grams of precursor powder was pelletized at 16 tons/in 2 in a 1-inch diameter die.
  • the pelletized precursor was then placed in a copper foil covered ceramic boat, and the boat placed in a 1.5-inch diameter tube furnace.
  • the tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon.
  • Argon gas was then purged at a constant 80 cc/min.
  • the furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 500 0 C at 2 °C/min, held at 500 0 C for 5 hrs, ramped to 700 0 C at 2 °C/min, and held at 700 0 C for 10 hrs.
  • the calcined product foamed up during calcination.
  • the Scherrer derived crystallite size is 46 nm and the carbon content is 9.5% (by combustion).
  • the DC electrical conductivity is 5.6 X 10 "6 S/cm (lHz).
  • Example 21 Ferric ammonium oxalate iron source and 1 mole % Zr doping 7.72 grams of etidronic acid solution (59% etidronic acid) was diluted with 50 ml of water. 1.64 grams of lithium carbonate was slowly added with stirring. After effervescence ceased, 150 ml of water was added. 16.85 grams of ferric ammonium oxalate and 0.255 grams of ammonium zirconium (IV) carbonate solution (15.1% Zr, stabilized with 1-2% tartaric acid) was dissolved in the solution. All dissolutions were performed at room temperature. After dissolution, the solution was poured into a Pyrex dish and dried at 130 0 C for 10 hrs.
  • etidronic acid solution 59% etidronic acid
  • the precursor was scraped from the dish into a mortar and briefly ground into a powder. 4 grams of precursor powder was pelletized at 16 tons/in 2 in a 1-inch diameter die. The pelletized precursor was then placed in a copper foil covered ceramic boat, and the boat placed in a 1.5-inch diameter tube furnace. The tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon. Argon gas was then purged at a constant 80 cc/min.
  • the furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 500 0 C at 2 °C/min, held at 500 0 C for 5 hrs, ramped to 700 0 C at 2 °C/min, and held at 700 0 C for 10 hrs.
  • the calcined product foamed up during calcination.
  • the Scherrer derived crystallite size is 48 nm and the carbon content is 9.3% (by combustion).
  • the DC electrical conductivity is 3.3 X 10 "5 S/cm (lHz).
  • Example 22 Ferric ammonium oxalate iron source and 1 mole % Ti doping
  • the furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 500 0 C at 2 °C/min, held at 500 0 C for 5 hrs, ramped to 700 0 C at 2 °C/min, and held at 700 0 C for 10 hrs.
  • the calcined product foamed up during calcination.
  • the Scherrer derived crystallite size is 47 nm and the carbon content is 9.8% (by combustion).
  • the DC electrical conductivity is 4 X 10 "5 S/cm (lHz).
  • Example 23 Ferric ammonium oxalate iron source and 1 mole % V doping 7.72 grams of etidronic acid solution (59% etidronic acid) was diluted with 50 ml of water. 1.64 grams of lithium carbonate was slowly added with stirring. After effervescence ceased, 150 ml of water was added. 16.85 grams of ferric ammonium oxalate and 0.14 grams ammonium vanadate was dissolved in the solution. All dissolutions were performed at room temperature. After dissolution, the solution was poured into a Pyrex dish and dried at 130 0 C for 10 hrs. After drying, the precursor was scraped from the dish into a mortar and briefly ground into a powder.
  • V 290.7690505 (all in angstroms).
  • the Scherrer derived crystallite size is 47 nm and the carbon content is 10% (by combustion).
  • the DC electrical conductivity is 1.1 X 10 "5 S/cm (lHz).
  • Example 24 Ferric ammonium oxalate iron source and 1 mole % Zr doping calcined at 525°C
  • the Scherrer derived crystallite size is 13nm and the carbon content is 10.5% (by combustion).
  • the DC electrical conductivity is 3.2 X 10 "9 S/cm (IHz).
  • Example 25 Ferric ammonium oxalate iron source and 1 mole % Ti doping calcined at 525°C
  • the Scherrer derived crystallite size is 14nm and the carbon content is 10.5% (by combustion).
  • the DC electrical conductivity is 1.6 X 10 9 S/cm (IHz).
  • Example 26 Ferric ammonium oxalate iron source and 1 mole % Ti doping calcined at 600 0 C 7.72 grams of etidronic acid solution (59% etidronic acid) was diluted with 50 ml of water. 1.64 grams of lithium carbonate was slowly added with stirring. After effervescence ceased, 150 ml of water was added. 16.85 grams of ferric ammonium oxalate and 0.255 grams of ammonium zirconium (IV) carbonate solution (15.1% Zr, stabilized with 1-2% tartaric acid) was dissolved in the solution. All dissolutions were performed at room temperature. After dissolution, the solution was poured into a Pyrex dish and dried at 130 0 C for 10 hrs.
  • etidronic acid solution 59% etidronic acid
  • the precursor was scraped from the dish into a mortar and briefly ground into a powder. 4 grams of precursor powder was pelletized at 16 tons/in 2 in a 1-inch diameter die. The pelletized precursor was then placed in a copper foil covered ceramic boat, and the boat placed in a 1.5-inch diameter tube furnace. The tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon. Argon gas was then purged at a constant 80 cc/min.
  • the furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 500 0 C at 2 °C/min, held at 500 0 C for 5 hrs, ramped to 600 0 C at 2 °C/min, and held at 600 0 C for 10 hrs.
  • the calcined product foamed up during calcination.
  • the Scherrer derived crystallite size is 18nm and the carbon content is 9.6% (by combustion).
  • the DC electrical conductivity is 4.5X 10 "8 S/cm (IHz).
  • Example 27 Ferric ammonium oxalate iron source and 1 mole % Zr doping calcined at 600 0 C
  • the Scherrer derived crystallite size is 16nm and the carbon content is 10.1 % (by combustion) .
  • the DC electrical conductivity is 9 X 10 8 S/cm S/cm ( 1 Hz) .
  • Example 28 Ferrous oxalate iron source and etidronic acid phosphorus source, 1 mole oxalic acid/mole Fe carbon additive, 1 mole % Zr doped and calcined at 700 0 C 7.72 grams of etidronic acid solution (59% etidronic acid) was diluted with 50 ml of water. 5.6 grams of oxalic acid was next added and dissolved. 1.64 grams of lithium carbonate was slowly added with stirring. After effervescence ceased, 150 ml of water was added. 7.95 grams of ferrous oxalate was added. Stirring was maintained at all times. 7 grams of 50% H 2 O 2 was slowly added.
  • the tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon. Argon gas was then purged at a constant 80 cc/min. The furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 500 0 C at 2 °C/min, held at 500 0 C for 5 hrs, ramped to 700 0 C at 2 °C/min, and held at 700 0 C for 10 hrs.
  • the Scherrer derived crystallite size is 34nm and the carbon content is 3.0% (by combustion).
  • the DC electrical conductivity is 1.2 X 10 "9 S/cm (IHz).
  • the solution was poured into a Pyrex dish and dried at 130 0 C for 5 hrs. After drying, the precursor was scraped from the dish into a mortar and briefly ground into a powder. 4 grams of precursor powder was pelletized at 16 tons/in 2 in a 1-inch diameter die. The pelletized precursor was then placed in a copper foil covered ceramic boat and the boat placed in a 1.5-inch diameter tube furnace. The tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon. Argon gas was then purged at a constant 80 cc/min.
  • the furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 400 0 C at 2 °C/min, add held at 400 0 C for 15 hrs.
  • the final product is amorphous based on X-ray Diffraction.
  • the carbon content is 4.9% (by combustion).
  • the DC electrical conductivity is 3.8 X 10 "10 S/cm (IHz).
  • Example 30 Ferrous oxalate iron source and etidronic acid phosphorus source, 1 mole oxalic acid/mole Fe carbon additive, 1 mole% Zr doped and calcined at 450 0 C
  • the solution was poured into a Pyrex dish and dried at 130 0 C for 5 hrs. After drying, the precursor was scraped from the dish into a mortar and briefly ground into a powder. 4 grams of precursor powder was pelletized at 16 tons/in 2 in a 1-inch diameter die. The pelletized precursor was then placed in a copper foil covered ceramic boat and the boat placed in a 1.5-inch diameter tube furnace. The tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon. Argon gas was then purged at a constant 80 cc/min. The furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 450 0 C at 2 °C/min, and held at 450 0 C for 15 hrs.
  • the Scherrer derived crystallite size is 28nm and the carbon content is 3.8% (by combustion).
  • the DC electrical conductivity is 2.0 X 10 "10 S/cm (IHz).
  • Example 31 Ferrous oxalate iron source and etidronic acid phosphorus source, 1 mole oxalic acid/mole Fe carbon additive, 1 mole % Zr doped and calcined at 525 0 C 7.72 grams of etidronic acid solution (59% etidronic acid) was diluted with 50 ml of water. 5.6 grams of oxalic acid was next added and dissolved. 1.64 grams of lithium carbonate was slowly added with stirring. After effervescence ceased, 150 ml of water was added. 7.95 grams of ferrous oxalate was added. Stirring was maintained at all times. 7 grams of 50% H 2 O 2 was slowly added.
  • the tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon. Argon gas was then purged at a constant 80 cc/min. The furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 525 0 C at 2 °C/min, and held at 525 0 C for 15 hrs.
  • the Scherrer derived crystallite size is 33nm.
  • the DC electrical conductivity is 1.8 X 10-9 S/cm (IHz).
  • Example 32 Mixed carboxylate precursor using 1.0 mole propionic acid /mole Fe, 1 mole % Zr doped and calcined at 525°C
  • the solution was poured into a Pyrex dish and dried at 130 0 C for 5 hrs. After drying, the precursor was scraped from the dish into a mortar and briefly ground into a powder. 4 grams of precursor powder was pelletized at 16 tons/in 2 in a 1-inch diameter die. The pelletized precursor was then placed in a copper foil covered ceramic boat, and the boat placed in a 1.5 -inch diameter tube furnace. The tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon. Argon gas was then purged at a constant 80 cc/min. The furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 525°C at 2 °C/min, and held at 525 0 C for 15 hrs.
  • the Scherrer derived crystallite size is 22nm and the carbon content is 8.2% (by combustion).
  • the DC electrical conductivity is 2.8 X 10 "9 S/cm (IHz).
  • Example 33 Mixed carboxylate precursor using 1.0 mole propionic acid /mole Fe and calcined at 450 0 C
  • the precursor was scraped from the dish into a mortar and briefly ground into a powder.
  • 4 grams of precursor powder was pelletized at 16 tons/in 2 in a 1-inch diameter die.
  • the pelletized precursor was then placed in a copper foil covered ceramic boat, and the boat placed in a 1.5-inch diameter tube furnace.
  • the tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon.
  • Argon gas was then purged at a constant 80 cc/min.
  • the furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 450 0 C at 2 °C/min, and held at 450 0 C for 15 hrs.
  • the Scherrer derived crystallite size is 24nm and the carbon content is 8.7% (by combustion).
  • the DC electrical conductivity is 5.0 X 10 ⁇ S/cm (IHz).
  • Example 34 Ferric ammonium oxalate iron source and 1 mole % Zr doping calcined at 450 0 C
  • the final product is amorphous, identified by X-ray Diffraction.
  • the carbon content is 11.6% (by combustion).
  • the DC electrical conductivity is 6.1 X 10 "10 S/cm (IHz).
  • Example 35 Mixed carboxylate precursor using 1.0 mole propionic acid /mole Fe, lmole % Zr doped and calcined at 600 0 C
  • the solution was poured into a Pyrex dish and dried at 130 0 C for 5 hrs. After drying, the precursor was scraped from the dish into a mortar and briefly ground into a powder. 4 grams of precursor powder was pelletized at 16 tons/in 2 in a 1-inch diameter die. The pelletized precursor was then placed in a copper foil covered ceramic boat, and the boat placed in a 1.5 -inch diameter tube furnace. The tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon. Argon gas was then purged at a constant 80 cc/min.
  • the furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 525°C at 2 °C/min, held at 525°C for 5 hrs, ramped to 600 0 C at 2 °C/min, and held at 600 0 C for 10 hrs.
  • the Scherrer derived crystallite size is 23nm and the carbon content is 8.5% (by combustion).
  • the DC electrical conductivity is 8.2 X 10 "9 S/cm (IHz).
  • Example 36 Mixed carboxylate precursor using 1.0 mole propionic acid/mole Fe, 1 mole % Zr doped and calcined at 700 0 C
  • the solution was poured into a Pyrex dish and dried at 130 0 C for 5 hrs. After drying, the precursor was scraped from the dish into a mortar and briefly ground into a powder. 4 grams of precursor powder was pelletized at 16 tons/in 2 in a 1-inch diameter die. The pelletized precursor was then placed in a copper foil covered ceramic boat, and the boat placed in a 1.5 -inch diameter tube furnace. The tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon. Argon gas was then purged at a constant 80 cc/min.
  • the furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 525°C at 2 °C/min, held at 525°C for 5 hrs, ramped to 700 0 C at 2 °C/min, and held at 700 0 C for 10 hrs.
  • V 372.1284209 (all in angstroms).
  • the Scherrer derived crystallite size is 27nm and the carbon content is 8.0% (by combustion).
  • the DC electrical conductivity is 1.7 X 10 "6 S/cm (lHz).
  • a water-soluble single compound LiFePO 4 precursor can be prepared using an aqueous acid-base reaction of a lithium source such as lithium hydroxide, an iron source such as ferric citrate or ferric nitrate, and a phosphorus containing chelation agent such as etidronic acid CH 3 C(OH)[PO(OH) 2 ]2 which contains 4 acid groups capable of an acid-base reaction with lithium and a chelation reaction with iron.
  • the resulting precursor contains ferric cations that are subsequently reduced to ferrous cations by a carbothermal reaction with carbon within the precursor molecule.
  • the final products were a carbon containing LiFePO 4 designated as LiFePO 4 -C where c is the percentage of carbon. Without being limited by theory, it was believed the reactions can be illustrated as follows (stoichiometrically assuming no excess carbon):
  • Ferric citrate source a. 6LiOH + 6FeC 6 H 5 O 7 + 3CH 3 C(OH)[PO(OH) 2 ] 2 -> Li 6 Fe 6 3[[CH 3 C(OH)[PO(O) 2 ] 2 ]][C 6 H 5 O 7 ] 4 + 6H 2 O + 2C 6 H 8 O 7
  • step a the solution was dried at 130 0 C, resulting in an intimate mixture of Li 6 Fe63[[CH 3 C(OH)[PO(O) 2 ] 2 ]][C6H 5 ⁇ 7]4 and citric acid.
  • step b both of these compounds are calcined, and during calcination Li, P and Fe remain mixed at the molecular level.
  • Li, P and Fe remain mixed at the molecular level.
  • Ferric nitrate source a. 2LiOH + 2Fe(NO 3 ) 3 + CH 3 C(OH)[PO(OH) 2 ] 2 ->
  • step a the solution was dried at 100 0 C resulting in Li 2 Fe 2 CH 3 C(OH)[PO(O) 2 ] 2 (NO 3 ) 4 and HNO 3 .
  • step b both of these compounds are calcined, and during calcination Li, P and Fe remain mixed at the molecular level.
  • LiFePO 4 produced using a phosphorus-containing chelation agent and ferric citrate produces LiFePO 4 with a high carbon content of 17.5% (Comparative Example 1). This high carbon content can reduce the intrinsic gravimetric electrochemical capacity of an electrode containing this LiFePO 4 product.
  • LiFePO 4 produced using a phosphorus-containing chelation agent and ferric nitrate can cause an explosive reaction, possibly between the nitrate moiety and the organic components of the precursor.
  • This reaction was illustrated by a DSC analysis (FIG. 2) of the LiFePO 4 precursor produced by the aqueous reaction of etidronic acid, lithium carbonate and ferric nitrate, followed by drying at 100 0 C, then pelletized at 17 tons/in 2 (Comparative Example 2). The precursor exploded at 150 0 C.
  • Comparative Example 1 Ferric citrate iron source 7.72 grams of etidronic acid solution (59% etidronic acid) was diluted with 50 ml of water. 1.64 grams of lithium carbonate was slowly added with stirring. After effervescence ceased, 150 ml of water was added. 11.75 grams of ferric citrate was dissolved in the solution at 60 0 C. After dissolution, the solution was poured into a Pyrex dish and dried at 130 0 C for 10 hrs. After drying, the precursor was scraped from the dish into a mortar and briefly ground into a powder. 4 grams of precursor powder was pelletized at 16 tons/in 2 in a 1-inch diameter die.
  • the pelletized precursor was then placed in a copper foil covered ceramic boat, and the boat placed in a 1.5-inch diameter tube furnace.
  • the tube furnace was vacuum evacuated 3 times, the last evacuation being for 15 minutes, and back filled with argon.
  • Argon gas was then purged at a constant 80 cc/min.
  • the furnace was heated from room temperature to 200 0 C at 5 °C/min, held at 200 0 C for 2 hrs, ramped to 500 0 C at 2 °C/min, held at 500 0 C for 5 hrs, ramped to 700 0 C at 2 °C/min, and held at 700 0 C for 10 hrs.
  • the Scherrer derived crystallite size was 49 nm and the carbon content was 17.5% (by combustion).
  • the DC electrical conductivity was l.l X 10 "3 S/cm (lHz).
  • Comparative Example 2 Ferric nitrate iron source 7.72 grams of etidronic acid solution (59% etidronic acid) was diluted with 50 ml of water. 1.64 grams of lithium carbonate was slowly added with stirring. After effervescence ceased, 150 ml of water was added. 17.9 grams of ferric nitrate was dissolved in the solution at 60 0 C. After dissolution, the solution was poured into a Pyrex dish and dried at 100 0 C for 10 hrs. After drying, the precursor was scraped from the dish into a mortar and briefly ground into a powder. 4 grams of precursor powder was pelletized at 16 tons/in 2 in a 1-inch diameter die. The pellet was heated in a differential scanning calorimeter under argon gas flow from room temperature to 600 0 C. The pelletized precursor exploded at 150 0 C as shown in FIG. 2. Other embodiments are within the scope of the following claims.

Abstract

L'invention concerne un procédé qui comprend la combinaison d'une source de lithium, d'une source de phosphore et d'une source de fer dans une solution aqueuse, la formation de LiFePO4 à partir de la solution et la formation d'une électrode comprenant le LiFePO4. Le LiFePO4 a moins d'approximativement 15 % en poids de carbone.
PCT/US2008/068321 2007-06-26 2008-06-26 Composés de phosphate de métal et batteries contenant ceux-ci WO2009003093A1 (fr)

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CN102227023A (zh) * 2011-05-16 2011-10-26 李朝林 一种磷酸铁锂前驱体及其制备方法
CN102593462A (zh) * 2012-03-15 2012-07-18 何劲松 一种碳包覆制备磷酸铁锂的方法
CN102897741A (zh) * 2011-07-26 2013-01-30 南京大学 一种纳米磷酸铁锂的水热制备方法
EP2608295A1 (fr) * 2011-12-23 2013-06-26 Samsung SDI Co., Ltd. Matériau actif positif pour batterie au lithium rechargeable, procédé de préparation de celui-ci, et batterie au lithium rechargeable comprenant celui-ci
CN104058138A (zh) * 2013-03-20 2014-09-24 东洋自动机株式会社 向附带气囊的袋子封入气体的方法及封入气体的装置
EP2835849A4 (fr) * 2012-04-05 2015-11-25 Hitachi Metals Ltd Procédé de fabrication de matériau actif d'électrode positive pour batteries secondaires non aqueuses, électrode positive pour batteries secondaires non aqueuses, et batterie secondaire non aqueuse
WO2016207827A1 (fr) * 2015-06-23 2016-12-29 University Of South Africa Procédé sol-gel pour lifepo4/c nanométrique destiné à des batteries haute performance au lithium-ion
CN112768664A (zh) * 2021-01-27 2021-05-07 重庆工商大学 一种钌掺杂的磷酸铁锂复合正极材料的制备方法
CN113264514A (zh) * 2021-05-17 2021-08-17 天津森特新材料科技有限责任公司 一种锂离子电池正极材料磷酸铁锂的制备方法
CN114835099A (zh) * 2022-04-21 2022-08-02 中国科学院过程工程研究所 一种废磷酸铁锂的再生利用方法及再生利用***装置
US11677077B2 (en) 2017-07-19 2023-06-13 Nano One Materials Corp. Synthesis of olivine lithium metal phosphate cathode materials

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102227023A (zh) * 2011-05-16 2011-10-26 李朝林 一种磷酸铁锂前驱体及其制备方法
CN102897741A (zh) * 2011-07-26 2013-01-30 南京大学 一种纳米磷酸铁锂的水热制备方法
EP2608295A1 (fr) * 2011-12-23 2013-06-26 Samsung SDI Co., Ltd. Matériau actif positif pour batterie au lithium rechargeable, procédé de préparation de celui-ci, et batterie au lithium rechargeable comprenant celui-ci
CN102593462A (zh) * 2012-03-15 2012-07-18 何劲松 一种碳包覆制备磷酸铁锂的方法
EP2835849A4 (fr) * 2012-04-05 2015-11-25 Hitachi Metals Ltd Procédé de fabrication de matériau actif d'électrode positive pour batteries secondaires non aqueuses, électrode positive pour batteries secondaires non aqueuses, et batterie secondaire non aqueuse
CN104058138A (zh) * 2013-03-20 2014-09-24 东洋自动机株式会社 向附带气囊的袋子封入气体的方法及封入气体的装置
WO2016207827A1 (fr) * 2015-06-23 2016-12-29 University Of South Africa Procédé sol-gel pour lifepo4/c nanométrique destiné à des batteries haute performance au lithium-ion
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US11677077B2 (en) 2017-07-19 2023-06-13 Nano One Materials Corp. Synthesis of olivine lithium metal phosphate cathode materials
CN112768664A (zh) * 2021-01-27 2021-05-07 重庆工商大学 一种钌掺杂的磷酸铁锂复合正极材料的制备方法
CN113264514A (zh) * 2021-05-17 2021-08-17 天津森特新材料科技有限责任公司 一种锂离子电池正极材料磷酸铁锂的制备方法
CN114835099A (zh) * 2022-04-21 2022-08-02 中国科学院过程工程研究所 一种废磷酸铁锂的再生利用方法及再生利用***装置

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