WO2014126566A1 - Sol-gel method for preparation of ceramic material - Google Patents
Sol-gel method for preparation of ceramic material Download PDFInfo
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- WO2014126566A1 WO2014126566A1 PCT/US2013/026093 US2013026093W WO2014126566A1 WO 2014126566 A1 WO2014126566 A1 WO 2014126566A1 US 2013026093 W US2013026093 W US 2013026093W WO 2014126566 A1 WO2014126566 A1 WO 2014126566A1
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- C01G45/1242—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]-, e.g. LiMn2O4, Li[MxMn2-x]O4
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Definitions
- the present invention relates to a process for forming ceramic materials, and particularly to a process for forming ceramic materials via a sol-gel process, and more particularly to a process for forming ceramic materials suitable for use as a cathode material in a lithium ion battery, via a sol-gel process.
- lithium transition metal oxides stand out as the most successful category of such cathode material.
- the crystal structures of lithium transition metal oxides can be a layered structure with a chemical formula of LiMO2 (M: Mn, Co, and Ni, etc.) and a three dimensional spinel structure with a typical chemical formula of LiM 2 O4 (M: Mn). Both the layered structure and the spinel structure are built up by transition metal and oxygen to form the framework, among which the lithium ions are intercalated.
- sol-gel methods apparently offer a relatively simple and facile method, which either does not cause or causes fewer environmental problems.
- sol-gel methods require a step to drive off the water in the solution at relatively high temperature, in order to achieve the gel state. This driving off of water is actually a concentrating step, needed to achieve a high concentration of solids, so that the resulting mixture will easily turn into a gel upon heating.
- One major drawback is that, during this step, phase separation among different components is quite possible, even likely, and this results in various non-homogeneities from this procedure.
- the non-homogeneities may present as one or more of irregular element distribution, irregular morphology, irregular and/or broad particle size distribution and irregular, non-uniform stoichiometry, which stoichiometric problems are especially serious for dopants.
- Such non-homogeneities can result in a need for additional processing and/or production of inferior ceramic products.
- the present invention provides an elegant solution to these long-standing problems in the art.
- the present invention provides a sol-gel method for producing ceramic materials that can, in various embodiments: be carried out at room temperature without a separate step of solution concentration; ensure a high quality product having a high level of homogeneity of element distribution, especially trace dopant elements; provide better morphology; provide smaller particle size in a more narrow range of size distribution; and provide excellent, uniform
- the resulting ceramic material may be used in cathode materials, particularly for lithium ion batteries, to provide an improved product, but is not limited to such use.
- the process is broadly applicable to a wide range of metal salts or oxides for use in preparing ceramic materials.
- the invention described herein relates to a sol-gel method to prepare ceramic materials suitable for use, e.g., in manufacture of a wide range of ceramics, including, when lithium is present in the ceramic matrix, lithium ion battery cathodes, the method having one or more of the following advantages: (1 ) a room temperature sol-gel process; (2) no water removal needed during the sol-gel process; (3) a simple, one-step process; (4) an environmental-friendly process; (5) a uniform, fine particle formation; (6) a homogeneous material; (7) a homogeneous distribution of trace elements (dopants); (8) readily applicable for thin film formation; (9) readily applicable for manufacture of a wide range of cathode material.
- the present invention relates to a process for producing a ceramic material including:
- aqueous solution comprising at least one transition metal ion and one or more further transition metal ion and/or one or more additional ion; adding to the aqueous solution a quaternary ammonium or phosphonium hydroxide comprising at least one alkyl group containing about 8 or more carbon atoms to form a combined aqueous solution;
- the formed gel is transferred directly to the furnace without an intervening step of water or solvent removal.
- the one or more additional ion includes a lithium ion.
- the at least one transition metal ion comprises one or more ion from Group 3-12 of the lUPAC periodic table.
- the transition metal may be any transition metal that is known for use in ceramic materials. In one embodiment, the transition metal is one known for use in lithium ion batteries.
- the at least one additional ion includes one or more ion selected from B, Al, Sn, Zn, Mg, Ga, Zr, Si, Ge and Ti. In one embodiment, the additional ion is present in a dopant quantity in the ceramic material. ln one embodiment, the at least one alkyl group contains from about 8 to about 40 carbon atoms, or from 12 to about 20 carbon atoms, or about 16 carbon atoms or about 18 carbon atoms. In one embodiment, the quaternary ammonium or phosphonium hydroxide further comprises three lower alkyl groups having from 1 to less than 8 carbon atoms, or from 1 to 4 carbon atoms.
- the quaternary ammonium or phosphonium in one embodiment, the quaternary ammonium or phosphonium
- hydroxide comprises two alkyl groups containing from about 8 to about 40 carbon atoms, or from 12 to about 20 carbon atoms, or about 16 or 18 carbon atoms.
- the quaternary ammonium or phosphonium hydroxide further comprises two lower alkyl groups having from 1 to less than 8 carbon atoms, or from 1 to 4 carbon atoms.
- the at least one alkyl group containing about 8 or more carbon atoms is unbranched.
- the heating is conducted with stepwise increases to a final temperature in the range from about 750°C to about 1000°C. In one embodiment, the heating is conducted in four steps, each step at a temperature greater than the previous step. In one embodiment, the heating is carried out for a total time of about 20 hours or more.
- any one or more of the foregoing embodiments may be combined with any one or more of the other of the foregoing embodiments, and the resulting combinations are all considered to fall within the scope of the disclosed and claimed invention.
- Fig. 1 is a schematic diagram of a first possible, theoretical mechanism of association of nitrate ions with quaternary ammonium molecules having a long alkyl chain, in accordance with an embodiment of the present invention.
- Fig. 2 is a schematic diagram of a second possible, theoretical
- FIG. 3 is a schematic diagram of a third possible, theoretical mechanism of association of transition metal ions, nitrate ions and quaternary ammonium molecules having a long alkyl chain, in accordance with an embodiment of the present invention.
- Figs. 4-14 are X-ray diffraction spectra of ceramic materials made in accordance with the present invention.
- Fig. 15 is a X-ray diffraction spectrum of commercially available lithium manganese oxide, a ceramic material of the prior art.
- Fig. 16-18 are SEM photographs of lithium transition metal oxide ceramic materials made in accordance with embodiments of the present invention.
- Fig. 19 is a SEM photograph of commercially available lithium
- a dopant quantity when used to describe the amount of an additional ion to be added to the aqueous solution and incorporated into the ceramic product to modify one or more of its properties, is an amount equal to or less than about 0.1 mole fraction of the elements present in the empirical formula other than the oxygen, where the total mole fraction of the elements present in the empirical formula other than oxygen is equal to one.
- the foregoing formula may include additional metals, e.g., M 4 , M 5 , etc., and additional dopants and, if so, their mole fraction is included in the total equal to 1 , and each dopant quantity remains equal to or less than 0.1 mole fraction.
- additional metals e.g., M 4 , M 5 , etc.
- additional dopants e.g., M 4 , M 5 , etc.
- the resultant ceramic material may be suitable for use as the cathode in a lithium ion battery.
- metal refers to both metals and to metalloids such as carbon, silicon and germanium, whether in an elemental or ionic state.
- the present invention relates to a process for producing a ceramic material including at least the following steps:
- aqueous solution comprising at least one transition metal ion and one or more further transition metal ion and/or one or more additional ion; adding to the aqueous solution a quaternary ammonium or phosphonium hydroxide comprising at least one alkyl group containing about 8 or more carbon atoms to form a combined aqueous solution;
- the formed gel is transferred directly to the furnace without an intervening step of water or solvent removal.
- the one or more additional ion includes a lithium ion.
- the at least one transition metal ion comprises one or more ion from Group 3-12 of the lUPAC periodic table.
- the transition metal may be any transition metal that is known for use in ceramic materials. In one embodiment, the transition metal is one known for use in lithium ion batteries.
- the additional ion comprises B, Al, Sn, Zn, Mg, Ga,
- the additional ion is different from the transition metal ion(s) present in the ceramic material.
- the additional ion is present in the ceramic material in a dopant quantity, as defined herein.
- any of the foregoing additional ions are also transition metal ions, if the ion is present in a dopant quantity as defined herein, then it is a dopant ion, otherwise it is one of the aforementioned transition metal ions.
- the ceramic material according to the present invention may include a plurality of metal ions and metalloid ions.
- the foregoing formula may include additional metals, e.g., M 4 , M 5 , etc., and additional dopants and, if so, their mole fraction is included in the total that is equal to 1 , and each dopant quantity remains equal to or less than 0.1 mole fraction.
- additional metals e.g., M 4 , M 5 , etc.
- additional ions in dopant quantities may be included.
- each additional (dopant) ion present in dopant quantities has a mole fraction equal to or less than 0.1 of the total of all mole fractions (other than the oxygen), which is 1 .
- transition metal ions and additional ions may be provided to the process in the form of any suitable salt or oxide.
- the transition metal ions and the additional ions are provided as the nitrate salt. If the transition metal ion and additional ion are provide as oxides, and placed into a solution of nitric acid, the oxides are generally considered to be converted to the nitrate salt, due to the much larger nitrate ion content, and to the water molecule formation resulting from protonation of the oxide oxygen atoms. While other polyoxygen anions, such as sulfate (SO4 2 ), phosphate (PO4 3 ),
- pyrophosphate (P )etc could be used, nitrate (NO3 ), is preferred herein.
- the at least one alkyl group contains from about 8 to about 40 carbon atoms, or from 12 to about 20 carbon atoms, or about 16 carbon atoms or about 18 carbon atoms.
- the quaternary ammonium or phosphonium hydroxide further comprises three lower alkyl groups having from 1 to less than 8 carbon atoms, or from 1 to 4 carbon atoms.
- the quaternary ammonium or phosphonium in one embodiment, the quaternary ammonium or phosphonium
- hydroxide comprises two alkyl groups containing from 8 to about 40 carbon atoms, or from 12 to about 20 carbon atoms, or about 16 or 18 carbon atoms.
- the quaternary ammonium or phosphonium hydroxide further comprises two lower alkyl groups having from 1 to less than 8 carbon atoms, or from 1 to 4 carbon atoms.
- the longer alkyl chain contains sixteen carbon atoms, is unbranched, and the other three alkyl groups are methyl groups, thus, the quaternary ammonium or phosphonium would be hexadecyltrimethyl ammonium (see, e.g., the Examples) or phosphonium hydroxide.
- any of the foregoing at least one alkyl group containing about 8 or more carbon atoms is unbranched.
- the quaternary ammonium or phosphonium molecule in the aqueous acidic medium in which the various ions are combined.
- the size of the other three or two alkyl groups on the quaternary ammonium or phosphonium molecule will also have some effect on this limitation, as will the branching or absence thereof, of the alkyl groups. That is, if the length and/or number of longer alkyl substituents is too great, the resulting quaternary ammonium or phosphonium molecule may not be sufficiently soluble.
- the actual, practical limit on the size of the alkyl group containing from 8 to about 40 carbon atoms, as well as whether there is one or two such substituents, is the solubility of the resulting quaternary ammonium or phosphonium molecule.
- the first of the three primary associations is between the negatively charged nitrate ion and the positively charged quaternary ammonium or phosphonium ion.
- the second of the three primary associations is the intermolecular interaction between the long alkyl groups of adjacent quaternary ammonium and/or phosphonium molecules, which provides a sort of "crosslinking" point between the adjacent quaternary ammonium and/or phosphonium molecules. It is this "crosslinking" that is considered to provide the binding force to maintain the gel formed in accordance with the present invention.
- crosslinking is in quotation marks to indicate that this is generally not a chemical bond-based crosslinking, in which an actual covalent bond would be formed between the alkyl groups on adjacent quaternary ammonium and/or phosphonium molecules, but is instead the type of association between adjacent long-chain alkyl groups that occurs in micelle formation in surfactant-containing aqueous solutions. That said, it is considered that, in the present invention, the intermolecular interactions are not actual micelle-forming interactions, but that the interactions are similar to those schematically depicted in Figs. 1 and 2, which are described in more detail below. As suggested by the schematic depictions in Figs.
- the third of the three primary associations is between the nitrate ions and the transition metal ions and additional ions, as depicted in Fig. 3.
- Fig. 1 is a schematic diagram of a first possible, theoretical mechanism of association of nitrate ions with quaternary ammonium molecules having a long alkyl chain, in accordance with an embodiment of the present invention.
- the associations depicted in Fig. 1 may be the initial association obtained upon mixing the nitrate ions with the quaternary ammonium ions.
- Fig. 2 is a schematic diagram of a second possible, theoretical
- the associations depicted in Fig. 2 may be the later, more developed association obtained some time after mixing the nitrate ions with the quaternary ammonium ions.
- Fig. 3 is a schematic diagram of a third possible, theoretical mechanism of association of transition metal ions, nitrate ions and quaternary ammonium molecules having a long alkyl chain, in accordance with an embodiment of the present invention.
- the associations depicted in Fig. 3 are believed to more correctly depict the various associations between lithium ions, transition metal ions, quaternary ammonium or phosphonium ions and counterions that were associated with the quaternary ammonium or phosphonium ions and, if so provided, with the transition metal ions and additional ions.
- the "crosslinking" between the respective quaternary ammonium long alkyl chains is depicted in Fig. 3 as the shaded circles or balls, and is schematic only, there being no intention to show this relationship as a ball or sphere, but rather simply to indicate that the long alkyl chains are "crosslinked” or intimately associated with each other.
- the process is usually carried out by first combining the various transition metal salts or oxides, lithium salt(s), optionally dopant salts or oxides, and water, to afford an aqueous solution of these salts. If the salts are added as the nitrate salts, it is not necessary separately to add another source of nitrate ions, such as nitric acid.
- the heating is conducted with stepwise increases to a final temperature in the range from about 750°C to about 1000°C. In one embodiment, the heating is conducted in four steps, each step at a temperature greater than the previous step. In one embodiment, the heating is carried out for a total time of about 20 hours or more.
- salts of lithium if present
- salts of the selected transition metals if present
- salts of any additional and/or dopant elements to be included are combined in water and stirred until thoroughly dissolved (usually overnight), when a clear solution is obtained.
- the thus-formed gel can be immediately and directly placed into a furnace for calcining, without any further concentration or removal of water. In the furnace, the temperature is gradually ramped up in a stepwise fashion.
- a typical, exemplary ramping procedure with hold times at various temperatures in the calcining process is the following:
- the exact times and temperatures used may be varied, provided that the gel is thoroughly calcined. The ramping helps to bring through the changes, to form a nascent ceramic and finally a fully calcined ceramic material.
- the present invention is broadly applicable for production of ceramic materials, and is particularly useful for preparation of ceramic materials suitable for use in cathode materials for lithium ion batteries.
- lithium nickel manganese cobalt oxide LiNio.33Mno.33Coo.33O2 lithium nickel cobalt aluminum oxide, LiNio.8Coo.15Alo.05O2
- lithium nickel cobalt aluminum oxide LiNio.79Coo.20Alo.01O2
- lithium nickel cobalt oxide LiNio.8Coo.2O2
- lithium titanate Li 2 TiO 3
- lithium cobalt manganese oxide LiCoo.sMno.2O2 lithium nickel manganese oxide, LiNio.85Mno.15O2
- lithium cobalt nickel manganese oxide LiCoo.45Nio.45Mno.10O2
- lithium nickel manganese oxide LiNio.sMno.2O2
- lithium nickel cobalt boron oxide LiNio.79Coo.2Bo.01O2
- lithium nickel cobalt tin oxide LiNio.79Coo.2Sno.01O2
- lithium nickel cobalt aluminum oxide LiNio.72Coo.2Bo.08O2
- oxide compounds formed in accordance with the present invention can be generalized, and some exemplary compounds are shown in the following:
- lithium nickel cobalt oxide LiNi x Coi -x O2
- lithium cobalt manganese oxide LiCo x Mni -x O2
- lithium nickel manganese oxide LiNi x Mni -x O2
- lithium cobalt nickel manganese oxide LiCo x Ni y Mn z O2
- the various doped compounds are shown with a single dopant ion. This is for illustrative purposes only and, as will be recognized, more than one dopant ion may be added to any of the foregoing compounds.
- the foregoing compounds are ceramic materials that may be made according to various embodiments of the present invention, and as further described herein and illustrated in several of the above-listed compounds, can include dopants added to slightly vary the above-indicated stoichiometry and the resulting properties of the ceramic material thus produced.
- a doped ceramic is the above-listed lithium nickel cobalt aluminum oxide
- LiNio.8Coo.15Alo.05O2 which contains a dopant quantity of aluminum (less than about 0.1 mole fraction) in addition to the lithium, nickel, cobalt and oxygen that would otherwise be present in un-doped lithium nickel cobalt oxide,
- the lithium ceramic material for use in lithium ion battery cathode may be a compound having one of the following formulae:
- Li x Nii -y CoO2 wherein 0.9 ⁇ x ⁇ 1 .1 and 0 ⁇ y ⁇ 1 .0;
- M 1 is one of Li, B, Mg, Al, Ti, Cr, Fe, Co, Ni, Cu, Zn, Ga, Y, F, I and S;
- Li m Mn 2-n M 2 n O2 wherein M 2 is a transition metal, 0.9 ⁇ m ⁇ 1 .1 and 0 ⁇ n ⁇ 1 .0.
- the quantity of water in which the transition metal compounds, dopant metal compounds and lithium compounds are initially dissolved can be varied as needed.
- the quantity of water should be as low as possible, just enough to provide complete dissolution of all of the transition metal and/or additional compounds and any other species added to the solution. In general, the less water present, the better the results from the gel formed.
- the solution obtained by dissolving the selected transition metal compounds, dopant compounds and lithium compounds is saturated or as close to saturation as can be achieved consistent with complete and timely dissolution.
- the as-prepared transition metal salt solution, or mixed transition metal salts solution preferably with nitrate as the salt counterion to the metal ion, includes a nitrate ion associated with a quaternary ammonium or phosphonium cations having at least one alkyl group containing about 8 to about 40 carbon atoms to afford a transition metal or mixed transition metal polyanion salt, as illustrated in Figs. 1 -3.
- the long aliphatic chain on the quaternary amnnoniunn or phosphoniunn cation can form strong intermolecular interactions as depicted in Figs. 1 -3, affording crosslinking or association between the alkyl groups containing the about 8 to about 40 carbon atoms.
- the as-obtained sol-gel is directly heated to high temperature to accomplish calcination and to form a ceramic material having improved properties.
- a ceramic material suitable for use as the cathode in a lithium ion battery is thereby prepared.
- the production of the actual cathode for a lithium ion battery from the ceramic material can be accomplished by techniques known to those of skill in the art, and is beyond the scope of the present disclosure. As noted, the ceramic material may also be useful for other purposes for which ceramic materials are known.
- Example 1 Preparation of lithium nickel cobalt oxide LiCoo.2Nio.802 To a 100 ml plastic beaker with a magnetic stirring bar, is added 3.8908 g
- Fig. 15 is a X-ray diffraction spectrum of a commercially available lithium manganese oxide, a ceramic material of the prior art.
- Fig. 19 is a SEM photograph of a
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KR1020157023866A KR101770198B1 (en) | 2013-02-14 | 2013-02-14 | Sol-gel method for preparation of ceramic material |
SG11201506080QA SG11201506080QA (en) | 2013-02-14 | 2013-02-14 | Sol-gel method for preparation of ceramic material |
US14/765,909 US9981879B2 (en) | 2013-02-14 | 2013-02-14 | Gel method for preparation of ceramic material |
JP2015557978A JP6110957B2 (en) | 2013-02-14 | 2013-02-14 | Sol-gel method for preparing ceramic materials |
CN201380073019.2A CN104995153B (en) | 2013-02-14 | 2013-02-14 | Prepare the sol-gel method of ceramic material |
PCT/US2013/026093 WO2014126566A1 (en) | 2013-02-14 | 2013-02-14 | Sol-gel method for preparation of ceramic material |
EP13706386.3A EP2956425A1 (en) | 2013-02-14 | 2013-02-14 | Sol-gel method for preparation of ceramic material |
IL24055415A IL240554B (en) | 2013-02-14 | 2015-08-12 | Sol-gel method for preparation of ceramic material |
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WO1999031745A1 (en) * | 1997-12-18 | 1999-06-24 | Research Corporation Technologies, Inc. | Mesostructural metal oxide materials useful as an intercalation cathode or anode |
WO2006036610A1 (en) * | 2004-09-22 | 2006-04-06 | Exxonmobil Research And Engineering Company | BULK Ni-Mo-W CATALYSTS MADE FROM PRECURSORS CONTAINING AN ORGANIC AGENT |
US20070148065A1 (en) * | 2001-04-12 | 2007-06-28 | Weir Richard D | Method of preparing ceramic powders using chelate precursors |
WO2011039595A2 (en) * | 2009-09-30 | 2011-04-07 | Eni S.P.A. | Mixed oxides of transition metal, hydrotreatment catalysts obtained therefrom, and preparation process comprising sol -gel processes |
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US6071489A (en) | 1996-12-05 | 2000-06-06 | Samsung Display Device Co., Ltd. | Methods of preparing cathode active materials for lithium secondary battery |
KR100237311B1 (en) * | 1997-04-25 | 2000-01-15 | 손욱 | Method of manufacturing cathode active mass and made thereby |
US7544632B2 (en) * | 2004-09-22 | 2009-06-09 | Exxonmobil Research And Engineering Company | Bulk Ni-Mo-W catalysts made from precursors containing an organic agent |
CN102013475A (en) * | 2010-10-22 | 2011-04-13 | 秦波 | Method for preparing porous spherical Li(1-x)MxFe(1-y)Ny(PO4)([3+(alpha-1)x+(beta-2) y]/3)/C material |
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WO1999031745A1 (en) * | 1997-12-18 | 1999-06-24 | Research Corporation Technologies, Inc. | Mesostructural metal oxide materials useful as an intercalation cathode or anode |
US20070148065A1 (en) * | 2001-04-12 | 2007-06-28 | Weir Richard D | Method of preparing ceramic powders using chelate precursors |
WO2006036610A1 (en) * | 2004-09-22 | 2006-04-06 | Exxonmobil Research And Engineering Company | BULK Ni-Mo-W CATALYSTS MADE FROM PRECURSORS CONTAINING AN ORGANIC AGENT |
WO2011039595A2 (en) * | 2009-09-30 | 2011-04-07 | Eni S.P.A. | Mixed oxides of transition metal, hydrotreatment catalysts obtained therefrom, and preparation process comprising sol -gel processes |
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