CA2877556C - Mixed sulphate containing lithium-manganese-metal phosphate - Google Patents
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Abstract
The present invention relates to a sulphate containing mixed Lithium-manganese iron phosphate of formula LixFeyMn1-yM1-(y+z) (PO4)u(SO4)v wherein M is a metal selected from the group Co, Ni, Al, Mg, Sn, Pb, Nb,B, Cu, Cr, Mo, Ru, V, Ga, Ca, Sr, Ba, Ti, Zr, Cd and mixtures thereof and wherein 0.9 = x = 1.5, 0 = y < 1, and 0,5 = (y + z) = 1 and 0.0 < u = 1,0 and 0 < v = 0,25, a process for producing it as well as its use as cathode material in a secondary lithium-ion battery.
Description
Mixed Sulphate containing lithium-manganese-metal phosphate The present invention relates to a novel substituted sulphate containing lithium-manganese iron phosphate, a process for producing it as well as its use as cathode material in a secondary lithium-ion battery.
Since the publications by Goodenough et al. (J. Electrochem.
Soc., 144, 1188-1194, 1997) there has been significant interest in particular in using lithium iron phosphate as cathode material in rechargeable secondary lithium-ion batteries. Lithium iron phosphate, compared with conventional lithium compounds based on spinels or layered oxides, such as lithium manganese oxide, lithium cobalt oxide and lithium nickel oxide, offers higher safety properties in the delithiated state such as are required in particular for the use of batteries in future in electric cars, electrically powered tools etc.
Pure lithium iron phosphate material was improved by so-called "carbon coating" (Ravet et al., Meeting of Electrochemical Society, Honolulu, 17 - 31 October 1999, EP 1 084 182 B1), as an increased capacity and power capability of the carbon-coated material are achieved at room temperature (160 mAH/g).
In addition to customary solid-state syntheses (US 5,910,382 Cl or US 6,514,640 Cl), a hydrothermal synthesis for lithium iron phosphate with the possibility of controlling the size and morphology of the lithium iron phosphate particles was disclosed in WO 2005/051840.
Since the publications by Goodenough et al. (J. Electrochem.
Soc., 144, 1188-1194, 1997) there has been significant interest in particular in using lithium iron phosphate as cathode material in rechargeable secondary lithium-ion batteries. Lithium iron phosphate, compared with conventional lithium compounds based on spinels or layered oxides, such as lithium manganese oxide, lithium cobalt oxide and lithium nickel oxide, offers higher safety properties in the delithiated state such as are required in particular for the use of batteries in future in electric cars, electrically powered tools etc.
Pure lithium iron phosphate material was improved by so-called "carbon coating" (Ravet et al., Meeting of Electrochemical Society, Honolulu, 17 - 31 October 1999, EP 1 084 182 B1), as an increased capacity and power capability of the carbon-coated material are achieved at room temperature (160 mAH/g).
In addition to customary solid-state syntheses (US 5,910,382 Cl or US 6,514,640 Cl), a hydrothermal synthesis for lithium iron phosphate with the possibility of controlling the size and morphology of the lithium iron phosphate particles was disclosed in WO 2005/051840.
2 A disadvantage of lithium iron phosphate is in particular its redox couple Fe3-/Fe2+ which has a much lower redox potential vis-a-vis Li/Lit (3.45 V versus Li/Lit) than for example the redox couple Co3+/Co4+ in LiCo02 (3.9 V versus Li/Li+).
In particular lithium manganese phosphate LiMnPO4 is of interest in view of its higher Mn2+/Mn3+ redox couple (4.1 volt) versus Li/Lit. LiMnPO4 was also already disclosed by Goodenough et al., US 5,910,382.
However, the production of electrochemically active and in particular carbon-coated LiMnPO4 has proved to be very difficult.
The electrochemical properties of lithium manganese phosphate were improved by iron substitution of the manganese sites:
Herle et al. in Nature Materials, Vol. 3, pp. 147-151 (2004) describe lithium-iron and lithium-nickel phosphates doped with zirconium. Morgan et al. describes in Electrochem. Solid State Lett. 7 (2), A30-A32 (2004) the intrinsic lithium-ion conductivity in LixMPO4 (M = Mn, Fe, Co, Ni) olivines. Yamada et al. in Chem. Mater. 18, pp. 804-813, 2004 deal with the electrochemical, magnetic and structural features of Li.(MnyFel_ )PO4, which are also disclosed e.g. in W02009/009758.
Structural variations of Lix(MnyFel_y) PO4, i.e. of the lithiophilite-triphylite series, were described by Losey et al. The Canadian Mineralogist, Vol. 42, pp. 1105-1115 (2004).
The practical effects of the latter investigations in respect of the diffusion mechanism of deintercalation in Lix(MnyFel_ )PO4 cathode material are found in Molenda et al. Solid State Ionics 177, 2617-2624 (2006).
In particular lithium manganese phosphate LiMnPO4 is of interest in view of its higher Mn2+/Mn3+ redox couple (4.1 volt) versus Li/Lit. LiMnPO4 was also already disclosed by Goodenough et al., US 5,910,382.
However, the production of electrochemically active and in particular carbon-coated LiMnPO4 has proved to be very difficult.
The electrochemical properties of lithium manganese phosphate were improved by iron substitution of the manganese sites:
Herle et al. in Nature Materials, Vol. 3, pp. 147-151 (2004) describe lithium-iron and lithium-nickel phosphates doped with zirconium. Morgan et al. describes in Electrochem. Solid State Lett. 7 (2), A30-A32 (2004) the intrinsic lithium-ion conductivity in LixMPO4 (M = Mn, Fe, Co, Ni) olivines. Yamada et al. in Chem. Mater. 18, pp. 804-813, 2004 deal with the electrochemical, magnetic and structural features of Li.(MnyFel_ )PO4, which are also disclosed e.g. in W02009/009758.
Structural variations of Lix(MnyFel_y) PO4, i.e. of the lithiophilite-triphylite series, were described by Losey et al. The Canadian Mineralogist, Vol. 42, pp. 1105-1115 (2004).
The practical effects of the latter investigations in respect of the diffusion mechanism of deintercalation in Lix(MnyFel_ )PO4 cathode material are found in Molenda et al. Solid State Ionics 177, 2617-2624 (2006).
3 In most cases, an increase in specific capacity compared to the pure lithium manganese phosphate upon substitution of iron for manganese in lithium manganese phosphate is observed.
However, a plateau-like region occurs for the discharge curves at 3.5 volt vis-A-vis lithium (iron plateau), the length of which compared with pure LiMnPO4 increases as the iron content increases, which results in a loss of energy density compared to an ideal LiMnPO4 that would have the same capacity as a LiFePO4. (see Yamada et al. in the publication mentioned above). The slow kinetics (charge and discharge kinetics) of manganese-containing metal phosphates, in particular Lix(MnyFel_ )PO4 with y > 0.8, have so far made the use of these compounds for battery applications largely impossible. Compounds like LiMn0.56Fe0.33Zn0.lcPO4 or LiMn0.66Fec.33PO4 have been recently synthesized (DE 10 2010 006 077 Al) and have proven to show good capacity when used as active materials for cathodes in secondary lithium ion batteries.
However, synthesis of these compounds especially via wet chemistry methods or hydrothermal methods yields materials with large primary particles and a high lithium deficiency causing a negative impact such as a relatively low capacity of the related lithium cells.
The object of the present invention was therefore to provide novel lithium-manganese-iron-phosphate compounds which provide a high energy density when used as cathode material and provide further a high redox potential with a rapid kinetics in respect of charge and discharge processes and to avoid a large lithium deficiency in the stoichiometry.
This object is achieved by a substituted sulphate containing mixed lithium-manganese iron phosphate of formula
However, a plateau-like region occurs for the discharge curves at 3.5 volt vis-A-vis lithium (iron plateau), the length of which compared with pure LiMnPO4 increases as the iron content increases, which results in a loss of energy density compared to an ideal LiMnPO4 that would have the same capacity as a LiFePO4. (see Yamada et al. in the publication mentioned above). The slow kinetics (charge and discharge kinetics) of manganese-containing metal phosphates, in particular Lix(MnyFel_ )PO4 with y > 0.8, have so far made the use of these compounds for battery applications largely impossible. Compounds like LiMn0.56Fe0.33Zn0.lcPO4 or LiMn0.66Fec.33PO4 have been recently synthesized (DE 10 2010 006 077 Al) and have proven to show good capacity when used as active materials for cathodes in secondary lithium ion batteries.
However, synthesis of these compounds especially via wet chemistry methods or hydrothermal methods yields materials with large primary particles and a high lithium deficiency causing a negative impact such as a relatively low capacity of the related lithium cells.
The object of the present invention was therefore to provide novel lithium-manganese-iron-phosphate compounds which provide a high energy density when used as cathode material and provide further a high redox potential with a rapid kinetics in respect of charge and discharge processes and to avoid a large lithium deficiency in the stoichiometry.
This object is achieved by a substituted sulphate containing mixed lithium-manganese iron phosphate of formula
4 LiõFe,MnM1_(y+z) (PO4) (SO4) wherein M is a metal selected from the group consisting of Co, Ni, Al, Mg, Sn, Pb, Nb ,B, Cu, Cr, Mo, Ru, V, Ga, Ca, Sr, Ba, Ti, Zr, Cd and mixtures thereof and wherein:
0.9 x 1.5, 0 < y < 1, and 0.001 (y + x) 1 and 0.75 u < 1,0 and 0 < v 0,25.
Surprisingly it was found that the sulphate containing mixed lithium manganese iron phosphate compound(s) (or in the following "the material(s)") according to the invention have a higher specific capacity than sulphate free lithium manganese iron phosphates and have a very low lithium deficiency if at all as well as a small primary particle size.
The increase in specific capacity is in the range of about 5 to 15 % compared corresponding to prior art materials without the presence of sulphate. The total sulphur content as measured by ICP is in the range between 0.01 and 0.16 wt%
based on the total material weight. The material according to the Invention has a controlled stoichiometry even a small Li deficiency can be controlled and regulated according to the specific electronic properties of the material.
The lithium manganese iron phosphate according to the invention may be doped or non-doped.
The term 'a or the lithium manganese iron phosphate" means within the scope of this invention therefore that the lithium manganese metal phosphate is present both doped or non-doped.
0.9 x 1.5, 0 < y < 1, and 0.001 (y + x) 1 and 0.75 u < 1,0 and 0 < v 0,25.
Surprisingly it was found that the sulphate containing mixed lithium manganese iron phosphate compound(s) (or in the following "the material(s)") according to the invention have a higher specific capacity than sulphate free lithium manganese iron phosphates and have a very low lithium deficiency if at all as well as a small primary particle size.
The increase in specific capacity is in the range of about 5 to 15 % compared corresponding to prior art materials without the presence of sulphate. The total sulphur content as measured by ICP is in the range between 0.01 and 0.16 wt%
based on the total material weight. The material according to the Invention has a controlled stoichiometry even a small Li deficiency can be controlled and regulated according to the specific electronic properties of the material.
The lithium manganese iron phosphate according to the invention may be doped or non-doped.
The term 'a or the lithium manganese iron phosphate" means within the scope of this invention therefore that the lithium manganese metal phosphate is present both doped or non-doped.
5 "Non-doped" means pure, in particular phase-pure lithium manganese iron phosphate having the formula LixFe,Mni_y(PO4)-1(SO4)v wherein x, y, u and v have the same meanings as above.
"Doped" lithium manganese iron metal phosphate denotes a compound of the formula LiõFeyMni_yMi_(y+z) (PO4)u(SO4)v with x, Y, u, z and v as defined before, wherein an additional metal M is present.
As recited above M may he selected from the group consisting of Co, Ni, Al, Mg, Sn, Pb, Nb ,B, Cu, Cr, Mo, Ru, V. Ga, Ca, Sr, Ba, Ti, Zr, Cd and mixtures thereof. Preferably M
represents Co, Mg, Nb, Ni, Al, Zn and mixtures thereof and (y+z) has a value of being 0.5 and 0.001. Exemplary stoichiometric formulae are LixFeyMni_yMg1Hy+,)(PO4)u(SO4)v .
Li,<FeyMn4,Nbl_(y+z) (PO4) u (SO4) v LixFeyMnl_yCoi_(y+z) (PO4) ti (SO4) v LixFeylvIn4õZn4_(y+1)(PO4)u(SO4)v and (PO4) (SO4) .
LiõFeyMn1,(Zn, Mg) 1- (y+z) PO4) SO4) v with x, y, z, u and v having the same meanings as recited above.
In further embodiments of the invention, the metal M
represents Zn, Mg, Al or combinations thereof like (Zn, Mg), (Mg, Al) or (Zn, Al), in particular M is Zn. It has been surprisingly found that these electrochemically inactive dopants provide materials according to the invention with particularly high energy density and capacity compared to the non-doped materials according to the invention or to materials doped with other dopants when they are used as electrode materials.
"Doped" lithium manganese iron metal phosphate denotes a compound of the formula LiõFeyMni_yMi_(y+z) (PO4)u(SO4)v with x, Y, u, z and v as defined before, wherein an additional metal M is present.
As recited above M may he selected from the group consisting of Co, Ni, Al, Mg, Sn, Pb, Nb ,B, Cu, Cr, Mo, Ru, V. Ga, Ca, Sr, Ba, Ti, Zr, Cd and mixtures thereof. Preferably M
represents Co, Mg, Nb, Ni, Al, Zn and mixtures thereof and (y+z) has a value of being 0.5 and 0.001. Exemplary stoichiometric formulae are LixFeyMni_yMg1Hy+,)(PO4)u(SO4)v .
Li,<FeyMn4,Nbl_(y+z) (PO4) u (SO4) v LixFeyMnl_yCoi_(y+z) (PO4) ti (SO4) v LixFeylvIn4õZn4_(y+1)(PO4)u(SO4)v and (PO4) (SO4) .
LiõFeyMn1,(Zn, Mg) 1- (y+z) PO4) SO4) v with x, y, z, u and v having the same meanings as recited above.
In further embodiments of the invention, the metal M
represents Zn, Mg, Al or combinations thereof like (Zn, Mg), (Mg, Al) or (Zn, Al), in particular M is Zn. It has been surprisingly found that these electrochemically inactive dopants provide materials according to the invention with particularly high energy density and capacity compared to the non-doped materials according to the invention or to materials doped with other dopants when they are used as electrode materials.
6 PCT/EP2013/067038 In one embodiment of the substituted sulphate containing lithium manganese iron metal phosphate of the present invention LixFeyMnl-Y11-(y+z)(PO4)u(SO4)v, the value for [1-(y+z)]
is in the range of more than 0.02 to 0.20 and is 0.03, 0.05, 0.06, 0.07 and 0.1 in specific embodiments.
The amount of sulphate is in the range of 0 < v 0.25, preferably between 0 < v 0.012. Too much sulphate would result in a loss of Li-ion conductivity. The specific embodiments v is 0.006 or 0.010.
The substitution (or doping) by the metal cations that are in themselves electrochemically inactive seems to provide the very best results at values of 1-(y+z) - 0.03 - 0.15 0.01, preferably 0.03 - 0.1 0.01 with regard to energy density and capacity of the material according to the invention. Further specific embodiments are even values for [1-(y+z)] in the aforementioned ranges such as 0.05, 0.06, 0.07, 0.08, 0.09 and 0.1 0.01. It was found that a high manganese content with a relatively low iron content (i.e. more manganese than iron should be present) and a relatively high zinc and/or magnesium (or aluminium) content provide the best results in respect of energy density, which is particularly surprising in view of the electrochemically inactive character of magnesium and zinc. It was found that for compounds according to the invention such as LioAMn080Fe0.10Zn00(PO4)(SO4)om Li,DA51Y.Ino.56Fec34Zno.in(PO4)(SO4)o.oi and Li9.95Mn0.59Fe0.34Zn0.07 (PO4) (SO4) 0.01 and LiMn0.56Fe0A3Zno.1c(PO4) (SO4)0.01 the 4V plateau is longer than for Li0.95Mn0.59Fe034Zn0.07PO4 or Li0.80Mn0.56Fe0A3Zn0.10PO4 and the specific capacity is higher, which means an increase in energy density.
is in the range of more than 0.02 to 0.20 and is 0.03, 0.05, 0.06, 0.07 and 0.1 in specific embodiments.
The amount of sulphate is in the range of 0 < v 0.25, preferably between 0 < v 0.012. Too much sulphate would result in a loss of Li-ion conductivity. The specific embodiments v is 0.006 or 0.010.
The substitution (or doping) by the metal cations that are in themselves electrochemically inactive seems to provide the very best results at values of 1-(y+z) - 0.03 - 0.15 0.01, preferably 0.03 - 0.1 0.01 with regard to energy density and capacity of the material according to the invention. Further specific embodiments are even values for [1-(y+z)] in the aforementioned ranges such as 0.05, 0.06, 0.07, 0.08, 0.09 and 0.1 0.01. It was found that a high manganese content with a relatively low iron content (i.e. more manganese than iron should be present) and a relatively high zinc and/or magnesium (or aluminium) content provide the best results in respect of energy density, which is particularly surprising in view of the electrochemically inactive character of magnesium and zinc. It was found that for compounds according to the invention such as LioAMn080Fe0.10Zn00(PO4)(SO4)om Li,DA51Y.Ino.56Fec34Zno.in(PO4)(SO4)o.oi and Li9.95Mn0.59Fe0.34Zn0.07 (PO4) (SO4) 0.01 and LiMn0.56Fe0A3Zno.1c(PO4) (SO4)0.01 the 4V plateau is longer than for Li0.95Mn0.59Fe034Zn0.07PO4 or Li0.80Mn0.56Fe0A3Zn0.10PO4 and the specific capacity is higher, which means an increase in energy density.
7 In further embodiments of the present invention, the value for y in the mixed lithium manganese iron phosphate according to the invention is 0.05 - 0.4, preferably 0.1 - 0.4. Exemplary specific values are preferably 0.10 0.015, 0.15 0.015, 0.20 0.015, and in particular 0.33 and 0.34 0.15, specifically 0.35 0.015. These values, in particular in conjunction with the above-mentioned values for 1-(y+z) represent the most preferred compromise between energy density and rate capability of the material according to the invention.
This means that for example the compound Li0.95Mno.59FecI34Zno07(PO4)(SO4)0Alhas a good rate capability up to 200 during discharge comparable with that of LiFePO4 of the state of the art (e.g. available from Clariant Produkte (Deutschland) GmbH or Phostech Lithium Inc.), but in addition also an increase in energy density (approx. 15-% vis-a-vis LiFePO4 (measured against a lithium anode).
In embodiments of the invention, the atomic ratio Li/EF,_,m,+m is in the range of between 0.9 to 1.5 (which corresponds to the value of x). It has been found that mixed lithium manganese iron phosphates satisfying this requirement provide an especially high capacity. In further embodiments this value is in the range of 0.9 to 1.2.
In further embodiments of the present invention, the substituted sulphate containing lithium-manganese iron phosphate compounds also comprise carbon. The carbon Is particularly preferably evenly distributed throughout the substituted lithium-manganese iron metal phosphate. In other words, the carbon forms a type of matrix in which the lithium-manganese iron metal phosphate according to the invention is embedded. It makes no difference for the meaning of the term
This means that for example the compound Li0.95Mno.59FecI34Zno07(PO4)(SO4)0Alhas a good rate capability up to 200 during discharge comparable with that of LiFePO4 of the state of the art (e.g. available from Clariant Produkte (Deutschland) GmbH or Phostech Lithium Inc.), but in addition also an increase in energy density (approx. 15-% vis-a-vis LiFePO4 (measured against a lithium anode).
In embodiments of the invention, the atomic ratio Li/EF,_,m,+m is in the range of between 0.9 to 1.5 (which corresponds to the value of x). It has been found that mixed lithium manganese iron phosphates satisfying this requirement provide an especially high capacity. In further embodiments this value is in the range of 0.9 to 1.2.
In further embodiments of the present invention, the substituted sulphate containing lithium-manganese iron phosphate compounds also comprise carbon. The carbon Is particularly preferably evenly distributed throughout the substituted lithium-manganese iron metal phosphate. In other words, the carbon forms a type of matrix in which the lithium-manganese iron metal phosphate according to the invention is embedded. It makes no difference for the meaning of the term
8 "matrix" used here whether e.g. the carbon particles serve as "nucleation sites" for the Li,,FeyMni-yM1-(y+z)(PO4).L(SO4), according to the invention, i.e. whether these nucleate on the carbon, or whether, as in a particularly preferred development of the present invention, the individual particles of the lithium-manganese iron metal phosphate LiõFevMni-A¨(y+z)(PO4),(SO4), are covered in carbon, i.e. sheathed or in other words at least partially coated. Both variants are considered as equivalent according to the invention and fall under the above definition of the term "carbon comprising".
Important for the purpose of the present invention is merely that the carbon is evenly distributed in the substituted lithium-manganese iron phosphate LiõFeyMnl_y1/11_(y+,) (POI)u(SO4) according to the invention and forms a type of (three-dimensional) matrix. In embodiments of the present invention, the presence of carbon or a carbon matrix can make obsolete the further addition of electrically conductive additives such as e.g. conductive carbon black, graphite etc. when using the LixFeyMnl-vM1-(y+z) (PO4) ,(304), according to the invention as electrode material.
In a further embodiment of the invention, the proportion of carbon relative to the substituted lithium-manganese iron phosphate is 4 wt.-%, in further embodiments 2.5 wt.-%, in still further embodiments 5 2.2 wt.-% and in still further embodiments 2.0 wt.-%. Thus the best energy densities of the material according to the invention are achieved.
The sulphate containing lithium-manganese iron phosphate LiõFeyMni-A¨(y+z) (PO4) T(SO4)v according to the invention is preferably contained as active material in a cathode for a secondary lithium-ion battery. As stated, this cathode can also contain the Li,,FeyMnl-A¨(y+z) (PO4)u(SO4), according to the
Important for the purpose of the present invention is merely that the carbon is evenly distributed in the substituted lithium-manganese iron phosphate LiõFeyMnl_y1/11_(y+,) (POI)u(SO4) according to the invention and forms a type of (three-dimensional) matrix. In embodiments of the present invention, the presence of carbon or a carbon matrix can make obsolete the further addition of electrically conductive additives such as e.g. conductive carbon black, graphite etc. when using the LixFeyMnl-vM1-(y+z) (PO4) ,(304), according to the invention as electrode material.
In a further embodiment of the invention, the proportion of carbon relative to the substituted lithium-manganese iron phosphate is 4 wt.-%, in further embodiments 2.5 wt.-%, in still further embodiments 5 2.2 wt.-% and in still further embodiments 2.0 wt.-%. Thus the best energy densities of the material according to the invention are achieved.
The sulphate containing lithium-manganese iron phosphate LiõFeyMni-A¨(y+z) (PO4) T(SO4)v according to the invention is preferably contained as active material in a cathode for a secondary lithium-ion battery. As stated, this cathode can also contain the Li,,FeyMnl-A¨(y+z) (PO4)u(SO4), according to the
9 invention without further addition of a further conductive material such as e.g. conductive carbon black, acetylene black, Ketjen black, graphite etc. (in other words is free of added conductive agent), both in the case of the carbon-containing LixFeyMni_yM+,)(PO4)u(SO4)v according to the invention and the carbon-free LixFeyMnl_yMi_(y+z) (PO4)u(SO4),-In further preferred embodiments, the cathode according to the invention contains a further lithium-metal-oxygen compound.
This addition increases the energy density by up to approx. 10 - 15%, depending on the type of the further mixed lithium metal compound compared with cathodes which contain only the LixFeviMni_yMj_(y+2)(PO4),(SO4), according to the invention as the sole active material.
The further lithium-metal-oxygen compound is preferably selected from substituted or non-substituted LiCo02, LiMn204, Li(Ni,Mn,Co)1,02, Li(Ni,Co,A1)02 and LiNi02, as well as Li(Mn,Fe)PO4, LiFePO4, LiCoPO4, LiNiPO4 and mixtures thereof.
The object of the present invention is further achieved by a process for producing a mixed lithium-manganese iron phosphate according to the invention with the general formula LixFeyMnl_ y 1- (y+ z)(PO4),(SO4), comprising the following steps:
a. providing an aqueous mixture with a pH < 7.5 containing at least one Li starting compound, one Mn starting compound, one Fe starting compound, optionally one M starting compound, one P043- and one S042- starting compound until a precipitate or a suspension in aqueous solution forms, b. carrying out a dispersion or grinding treatment of the mixture and/or the suspension, c. obtaining LiõFe,Mnl_yMi_(y+z) (PO4)u(SO4), wherein x, y, z and v have the above referenced meanings, from the suspension by reaction under hydrothermal conditions 5 wherein a precipitate forms.
The treatment in step b. is preferably carried out until the DR value of the particles in the mixture is less than 50 pm, preferably at most 25 pm.
The term "hydrothermal conditions" means for the purpose of the present invention temperatures of 100 C to 200 C, preferably 100 C to 170 C and quite particularly preferably 120 C to 170 C as well as a pressure of 1 bar to 40 bar vapour pressure. In particular, it has surprisingly been shown that the synthesis at the quite particularly preferred temperature of 120 - 170 C, in particular at 160 5 C, leads to an increase in the specific capacity of the thus-obtained LixFeyMnl-vM1-(y+z) (PO4)-3(SO4), according to the invention compared with reaction at more than 170 C.
As stated before, the synthesis takes place in aqueous solution/suspension. At the end of the reaction, the pH of the reaction solution (i.e. after precipitation of the product Li,<FeyMni-v1\41-(y+z) (PO4)ti (SO4)v) is approx. 5 to 6.5, i.e. the reaction itself takes place in a non-basic or in other words in a weak acid environment.
The process according to the invention makes possible in particular the production of phase-pure LixFeyYlnI_A__ (y-Fz)(POdu(SO4), which means free of impurities to be determined by means of XRD.
A further aspect of the present invention is the provision of LixFevlAnl_yM1_(1,+(PO4)(SO4), which can be obtained by means of the process according to the invention and is compared to a solid state synthesis pathway phase-pure in the sense as mentioned before, i.e. especially no phosphide phases can be detected in the final product.
In embodiments of the process according to the invention, the dispersion or grinding treatment begins before or during the suspension formation and is continued until the suspension/precipitation is finished.
Preferably, the dispersion or grinding treatment starts before the suspension/precipitation of the mixture in order to bring about an increased nucleation and in order to prevent the formation of large crystals and crystal agglomerates.
After the hydrothermal treatment, the LixFeyMnl-yM1-(1,+(PO4)u(SO4)v obtained according to the invention is separated off by filtration and/or centrifuging as well as dried and, in preferred embodiments of the invention, disagglomerated in order to obtain a product consisting predominantly (ca. 95%) of primary particles, e.g. by grinding with an air-jet mill.
In specific embodiments of the process according to the invention, a carbon-containing material is added during step a) or c). This can be either pure carbon, such as e.g.
graphite, acetylene black or Ketjen black, or a carbon-containing precursor compound which then decomposes when exposed to the action of heat to a carbonaceous residue, e.g.
starch, gelatine, a polyol, a sugar such as mannose, fructose, sucrose, lactose, galactose, a partially water-soluble polymer such as e.g. a polyacrylate etc.
Alternatively, the LixFeõMnl_yMi__(PO4)u(SO4), obtained after the hydrothermal treatment can also be mixed with a carbon-containing material as defined above or impregnated with an aqueous solution of same. This can take place either directly after the isolation (filtration) of the LixFeõMnl_yMI_ (y+z) (PO4)u(SO4), or after it has been dried or disagglomerated.
For example the mixture of LiõFeyMni_yMi-(y+z)(PO4)u.(SO4)v and a carbon precursor compound (which was added e.g. during the process) or the LixFey]Mm_ybild(PO4)u(SO4)v impregnated with for a solution the carbon precursor compound (as for example sucrose or lactose) is then dried and heated at a temperature between 500 C and 850 C, wherein the carbon precursor compound is pyrolyzed to pure carbon which then wholly or at least partly covers the LixFeyMnl_yMl_iy+z) (PO4)u(SO4), particles as a layer (coating).
The pyrolysis can be followed by a grinding or disagglomeration treatment but the grinding step is not mandatory.
The LixFeõMhi_yM1_(s,+2)(PO4)-3(SO4)v obtained according to the process invention is preferably dried under protective gas, in air or under vacuum at temperatures of from 50 C to 200 C, preferably under protective gas and the pyrolysis preferably likewise under protective gas, preferably nitrogen.
Within the scope of the process according to the invention, the at least one Li source, the Fe2+ and Mn2-' sources as well as the MY- (y = 2, 3 or 4; for Nb and V, Mo y may be also 5) source(s) are preferably used in the form of aqueous solutions and the P043- and S042- sources in the form of a liquid, e.g. as H3PO4 or H2SO4 or as an aqueous solution or suspension of a solid phosphate and/or sulphate compound.
In preferred embodiments of the process according to the invention, the Li source is first dissolved in an aqueous solvent, the Fe2+, the Mn2+ and the Mr sources as well as the P043- and S042- source are then added and mixed under inert gas atmosphere. The reaction then takes place under hydrothermal conditions and preferably under protective gas.
According to the invention, Li2O, LiC1, LiNO3, Li0H, Li2SO4 or Li2CO3, preferably Li0H, Li2O, Li2SO4 or Li2CO3, is used as lithium source.
In further embodiments of the invention a second lithium source is used which is different from the first one.
Preferably the second lithium source is Li2S0 providing a cheap and simple source for sulphate consisting from the waste water when the process according to the invention is designed as a cyclic process as for example described in W02006/097324 or W02009/010263. If the first lithium source is already Li2SO4, then it is evident that the second one is not Li2SO4 but for example Li0H, Li2O ect.
The Fe source is preferably an Fe2+ salt, in particular FeSO4, FeCl2, FeNO3, Fe(PO4)2 or an Fe organyl salt or an iron carboxylate like iron oxalate, iron citrate, iron acetate etc.
The Mn source is preferably a water-soluble manganese (II) salt such as manganese sulphate, manganese acetate, manganese oxalate, manganese chloride, manganese nitrate, manganese hydroxide, manganese carbonate etc.
According to the invention, phosphoric acid, a metal phosphate, hydrogen phosphate or dihydrogen phosphate is preferably used as P043- source.
In particular, the corresponding sulphates, in particular of Mg, Zn and Ca, or the corresponding halides, nitrates, acetates, carboxylates, preferably the acetates and caboxylates may be used as source for the bivalent metal cation.
A further object of the present invention is the mixed lithium-manganese-metal phosphate of formula LiõFeyMni_yMi-(y+z) (PO4) u (SO4) , wherein M is a metal selected from the group Co, Ni, Al, Mg, Sn, Pb, Nb, B, Cu, Cr, Mo, Ru, V, Ga, Ca, Sr, Ba, Ti, Zr, Cd and mixtures thereof and wherein:
0.9 x 1.5, 0 y < 1, and 0.001 (y + z) 1 and 0.75 < u < 1.0 and 0 < v 0.25.
The invention is explained in more detail below with reference to examples and drawings which are not, however, to be considered as limiting the scope of the invention.
It is shown in:
Figure 1 discharge curves at 1C and at room temperature for Li0.80Mn0.56Fe0.33Zn0.10PO4 (Comparative Example 1);
Figure 2 discharge curves at 1C and at room temperature for Li0.99Mn0.56Fe0.33Zn0.10PO4 (SO4) 0.006 (Example 1) ;
Figure 3 discharge curves at 1C and at room temperature for Li0.99Mn0.56Fe0.33Zn0.10PO4 (SO4) 0.01 (Example 2) ;
14a Figure 4 discharge curves for at 10 at room temperature for Li0.80Mn0.59Fe0.34Zn0.07PO4;
Figure 5 discharge curves for at 10 at room temperature for Li0.91Mn0.59Fe0.34Zn0.07PO4 (SO4) o.oi;
Figure 6 SEM image of Li0.80Mn0.59Fe0.34Zno.07PO4;
Figure 7 SEM image of Li0.91Mn0.59Fe0.34Zn0.07PO4 (SO4) 0.01 Figure 8 discharge curves at 1C at room temperature for Lij.80Mn0.80Fe0. isZno o5PO4 5 Figure 9 discharge curves at 1C at room temperature for Lij.93Mn0.80Fe0.15Zn0.05PO4 (SO4) 0.01 Figure 10 SEM image of Lio.KINInD.80Fe0.15Zno.05POL
This addition increases the energy density by up to approx. 10 - 15%, depending on the type of the further mixed lithium metal compound compared with cathodes which contain only the LixFeviMni_yMj_(y+2)(PO4),(SO4), according to the invention as the sole active material.
The further lithium-metal-oxygen compound is preferably selected from substituted or non-substituted LiCo02, LiMn204, Li(Ni,Mn,Co)1,02, Li(Ni,Co,A1)02 and LiNi02, as well as Li(Mn,Fe)PO4, LiFePO4, LiCoPO4, LiNiPO4 and mixtures thereof.
The object of the present invention is further achieved by a process for producing a mixed lithium-manganese iron phosphate according to the invention with the general formula LixFeyMnl_ y 1- (y+ z)(PO4),(SO4), comprising the following steps:
a. providing an aqueous mixture with a pH < 7.5 containing at least one Li starting compound, one Mn starting compound, one Fe starting compound, optionally one M starting compound, one P043- and one S042- starting compound until a precipitate or a suspension in aqueous solution forms, b. carrying out a dispersion or grinding treatment of the mixture and/or the suspension, c. obtaining LiõFe,Mnl_yMi_(y+z) (PO4)u(SO4), wherein x, y, z and v have the above referenced meanings, from the suspension by reaction under hydrothermal conditions 5 wherein a precipitate forms.
The treatment in step b. is preferably carried out until the DR value of the particles in the mixture is less than 50 pm, preferably at most 25 pm.
The term "hydrothermal conditions" means for the purpose of the present invention temperatures of 100 C to 200 C, preferably 100 C to 170 C and quite particularly preferably 120 C to 170 C as well as a pressure of 1 bar to 40 bar vapour pressure. In particular, it has surprisingly been shown that the synthesis at the quite particularly preferred temperature of 120 - 170 C, in particular at 160 5 C, leads to an increase in the specific capacity of the thus-obtained LixFeyMnl-vM1-(y+z) (PO4)-3(SO4), according to the invention compared with reaction at more than 170 C.
As stated before, the synthesis takes place in aqueous solution/suspension. At the end of the reaction, the pH of the reaction solution (i.e. after precipitation of the product Li,<FeyMni-v1\41-(y+z) (PO4)ti (SO4)v) is approx. 5 to 6.5, i.e. the reaction itself takes place in a non-basic or in other words in a weak acid environment.
The process according to the invention makes possible in particular the production of phase-pure LixFeyYlnI_A__ (y-Fz)(POdu(SO4), which means free of impurities to be determined by means of XRD.
A further aspect of the present invention is the provision of LixFevlAnl_yM1_(1,+(PO4)(SO4), which can be obtained by means of the process according to the invention and is compared to a solid state synthesis pathway phase-pure in the sense as mentioned before, i.e. especially no phosphide phases can be detected in the final product.
In embodiments of the process according to the invention, the dispersion or grinding treatment begins before or during the suspension formation and is continued until the suspension/precipitation is finished.
Preferably, the dispersion or grinding treatment starts before the suspension/precipitation of the mixture in order to bring about an increased nucleation and in order to prevent the formation of large crystals and crystal agglomerates.
After the hydrothermal treatment, the LixFeyMnl-yM1-(1,+(PO4)u(SO4)v obtained according to the invention is separated off by filtration and/or centrifuging as well as dried and, in preferred embodiments of the invention, disagglomerated in order to obtain a product consisting predominantly (ca. 95%) of primary particles, e.g. by grinding with an air-jet mill.
In specific embodiments of the process according to the invention, a carbon-containing material is added during step a) or c). This can be either pure carbon, such as e.g.
graphite, acetylene black or Ketjen black, or a carbon-containing precursor compound which then decomposes when exposed to the action of heat to a carbonaceous residue, e.g.
starch, gelatine, a polyol, a sugar such as mannose, fructose, sucrose, lactose, galactose, a partially water-soluble polymer such as e.g. a polyacrylate etc.
Alternatively, the LixFeõMnl_yMi__(PO4)u(SO4), obtained after the hydrothermal treatment can also be mixed with a carbon-containing material as defined above or impregnated with an aqueous solution of same. This can take place either directly after the isolation (filtration) of the LixFeõMnl_yMI_ (y+z) (PO4)u(SO4), or after it has been dried or disagglomerated.
For example the mixture of LiõFeyMni_yMi-(y+z)(PO4)u.(SO4)v and a carbon precursor compound (which was added e.g. during the process) or the LixFey]Mm_ybild(PO4)u(SO4)v impregnated with for a solution the carbon precursor compound (as for example sucrose or lactose) is then dried and heated at a temperature between 500 C and 850 C, wherein the carbon precursor compound is pyrolyzed to pure carbon which then wholly or at least partly covers the LixFeyMnl_yMl_iy+z) (PO4)u(SO4), particles as a layer (coating).
The pyrolysis can be followed by a grinding or disagglomeration treatment but the grinding step is not mandatory.
The LixFeõMhi_yM1_(s,+2)(PO4)-3(SO4)v obtained according to the process invention is preferably dried under protective gas, in air or under vacuum at temperatures of from 50 C to 200 C, preferably under protective gas and the pyrolysis preferably likewise under protective gas, preferably nitrogen.
Within the scope of the process according to the invention, the at least one Li source, the Fe2+ and Mn2-' sources as well as the MY- (y = 2, 3 or 4; for Nb and V, Mo y may be also 5) source(s) are preferably used in the form of aqueous solutions and the P043- and S042- sources in the form of a liquid, e.g. as H3PO4 or H2SO4 or as an aqueous solution or suspension of a solid phosphate and/or sulphate compound.
In preferred embodiments of the process according to the invention, the Li source is first dissolved in an aqueous solvent, the Fe2+, the Mn2+ and the Mr sources as well as the P043- and S042- source are then added and mixed under inert gas atmosphere. The reaction then takes place under hydrothermal conditions and preferably under protective gas.
According to the invention, Li2O, LiC1, LiNO3, Li0H, Li2SO4 or Li2CO3, preferably Li0H, Li2O, Li2SO4 or Li2CO3, is used as lithium source.
In further embodiments of the invention a second lithium source is used which is different from the first one.
Preferably the second lithium source is Li2S0 providing a cheap and simple source for sulphate consisting from the waste water when the process according to the invention is designed as a cyclic process as for example described in W02006/097324 or W02009/010263. If the first lithium source is already Li2SO4, then it is evident that the second one is not Li2SO4 but for example Li0H, Li2O ect.
The Fe source is preferably an Fe2+ salt, in particular FeSO4, FeCl2, FeNO3, Fe(PO4)2 or an Fe organyl salt or an iron carboxylate like iron oxalate, iron citrate, iron acetate etc.
The Mn source is preferably a water-soluble manganese (II) salt such as manganese sulphate, manganese acetate, manganese oxalate, manganese chloride, manganese nitrate, manganese hydroxide, manganese carbonate etc.
According to the invention, phosphoric acid, a metal phosphate, hydrogen phosphate or dihydrogen phosphate is preferably used as P043- source.
In particular, the corresponding sulphates, in particular of Mg, Zn and Ca, or the corresponding halides, nitrates, acetates, carboxylates, preferably the acetates and caboxylates may be used as source for the bivalent metal cation.
A further object of the present invention is the mixed lithium-manganese-metal phosphate of formula LiõFeyMni_yMi-(y+z) (PO4) u (SO4) , wherein M is a metal selected from the group Co, Ni, Al, Mg, Sn, Pb, Nb, B, Cu, Cr, Mo, Ru, V, Ga, Ca, Sr, Ba, Ti, Zr, Cd and mixtures thereof and wherein:
0.9 x 1.5, 0 y < 1, and 0.001 (y + z) 1 and 0.75 < u < 1.0 and 0 < v 0.25.
The invention is explained in more detail below with reference to examples and drawings which are not, however, to be considered as limiting the scope of the invention.
It is shown in:
Figure 1 discharge curves at 1C and at room temperature for Li0.80Mn0.56Fe0.33Zn0.10PO4 (Comparative Example 1);
Figure 2 discharge curves at 1C and at room temperature for Li0.99Mn0.56Fe0.33Zn0.10PO4 (SO4) 0.006 (Example 1) ;
Figure 3 discharge curves at 1C and at room temperature for Li0.99Mn0.56Fe0.33Zn0.10PO4 (SO4) 0.01 (Example 2) ;
14a Figure 4 discharge curves for at 10 at room temperature for Li0.80Mn0.59Fe0.34Zn0.07PO4;
Figure 5 discharge curves for at 10 at room temperature for Li0.91Mn0.59Fe0.34Zn0.07PO4 (SO4) o.oi;
Figure 6 SEM image of Li0.80Mn0.59Fe0.34Zno.07PO4;
Figure 7 SEM image of Li0.91Mn0.59Fe0.34Zn0.07PO4 (SO4) 0.01 Figure 8 discharge curves at 1C at room temperature for Lij.80Mn0.80Fe0. isZno o5PO4 5 Figure 9 discharge curves at 1C at room temperature for Lij.93Mn0.80Fe0.15Zn0.05PO4 (SO4) 0.01 Figure 10 SEM image of Lio.KINInD.80Fe0.15Zno.05POL
10 Figure 11 SEM image of LiMn0A0Fe0.15Zno.05PO4(SO4)o.ol Figure 12 discharge curves at 1C at room temperature for LiMn0.61Fe034Zn0.05PO4 15 Figure 13 discharge curves at 1C at room temperature for L10.96Mn0.61Fe0.34Zn0.05PO4 (SO4) 0.01 Figure 14 SEM image of Lio.8014n9.61Feo.34ZncA5PO4 Figure 15 SEM image of Li0.96Mni.61Fe0.34ZncA5PO4(SO4)0.01 Figure 16 discharge curves at 1C at room temperature for LiD.80Mno. 63FeC 34Z no . 03PO4 Figure 17 discharge curves at 1C at room temperature for Li1.97Mn0.63Fe0.34Zn0.n3PO4 (SO4) n.u.
Examples 1. Determination of the particle-size distribution:
The particle-size distributions for the mixtures or suspensions and of the produced material is determined using the light scattering method using commercially available devices. This method is known per se to a person skilled in the art, wherein reference is also made in particular to the disclosure in JP 2002-151082 and WO 02/083555. In this case, the particle-size distributions were determined by a laser diffraction measurement apparatus (Mastersizer S. Malvern Instruments GmbH, Herrenberg, DE) and the manufacturer's software (version 2.19) with a Malvern Small Volume Sample Dispersion Unit, DIF 2002 as measuring unit. The following measuring conditions were selected: compressed range; active beam length 2.4 mm; measuring range: 300 RF; 0.05 to 900 pm.
The sample preparation and measurement took place according to the manufacturer's instructions.
The D(,0 value gives the value at which 90% of the particles in the measured sample have a smaller or the same particle diameter. Accordingly, the D50 value and the D10 value give the value at which 50% and 10% respectively of the particles in the measured sample have a smaller or the same particle diameter.
According to an embodiment according to the invention, the values mentioned in the present description are valid for the DK values, D50 values, the D90 values as well as the difference between the D90 and DK values relative to the volume proportion of the respective particles in the total volume. Accordingly, the DK, D50 and Dn values mentioned herein give the values at which 10 volume-% and 50 volume-% and 90 volume-% respectively of the particles in the measured sample have a smaller or the same particle diameter. If these values are obtained, particularly advantageous materials are provided according to the invention and negative influences of relatively coarse particles (with relatively larger volume proportion) on the processability and the electrochemical product properties are avoided. Preferably, the values mentioned in the present description are valid for the D10 values, the D50 values, the D90 values as well as the difference between the D90 and the D10 values relative to both percentage and volume percent of the particles.
For compositions (e.g. electrode materials) which, in addition to the lithium-manganese iron phosphates according to the invention are further doped with metal cations, contain further components, in particular for carbon-containing compositions, the above light scattering method can lead to misleading interpretations as the primary particles can form agglomerates within the suspension. However, the primary particle-size distribution of the material according to the invention can be directly determined as follows for such compositions using SEM photographs:
A small quantity of the powder sample is suspended in acetone and dispersed with ultrasound for 10 minutes. Immediately thereafter, a few drops of the suspension are dropped onto a sample plate of a scanning electron microscope (SEM). The solids concentration of the suspension and the number of drops are measured so that a large single-ply layer of powder particles forms on the support in order to prevent the powder particles from obscuring one another. The drops must be added rapidly before the particles can separate by size as a result of sedimentation. After drying in air, the sample is placed in the measuring chamber of the SEM. In the present example, this is a LEO 1530 apparatus which is operated with a field emission electrode at 1.5 kV excitation voltage and a 4 mm space between samples. At least 20 random sectional magnifications of the sample with a magnification factor of 20,000 are photographed. These are each printed on a DIN A4 sheet together with the inserted magnification scale. On each of the at least 20 sheets, if possible at least 10 free visible particles of the material according to the invention, from which the powder particles are formed together with the carbon-containing material, are randomly selected, wherein the boundaries of the particles of the material according to the invention are defined by the absence of fixed, direct connecting bridges. On the other hand, bridges formed by carbon material are included in the particle boundary. Of each of these selected particles, those with the longest and shortest axis in the projection are measured in each case with a ruler and converted to the actual particle dimensions using the scale ratio. For each measured particle, the arithmetic mean from the longest and the shortest axis is defined as particle diameter. The measured particles are then divided analogously to the light-scattering method into size classes.
The differential particle-size distribution relative to the number of particles is obtained by plotting the number of the associated particles in each case against the size class. The cumulative particle-size distribution from which Dlc, D50 and DK can be read directly on the size axis is obtained by continually totalling the particle numbers from the small to the large particle classes.
The described process was also applied to battery electrodes containing the material according to the invention. In this case, however, instead of a powder sample a fresh cut or fracture surface of the electrode is secured to the sample holder and examined under a SEM.
When producing the materials, it is to be borne in mind that the materials are precipitated from an aqueous Fe precursor solution. The reaction and drying/sintering is therefore preferably to be carried out under protective gas or vacuum in order to avoid a partial oxidation of Fe2+ to Fe '+ with formation of by-products such as Fe2O3 or FePO4.
Comparative Example 1:
Synthesis of Li0A0Mn0.56Fe0.33Zn0.10PO4 Production and precipitation/suspension of a precursor mixture First, 105.5 g lithium hydroxide LiOH = H20 was dissolved in 0.9 I distilled water. This solution is called basic solution.
77.43 g FeSO4 x 7 H20, 79.88 g MnSO4x H20 and 24.27 g ZnSO4 x 7 H20 were dissolved in approx. 1.5 I distilled water and 103.38 g 80-% phosphoric acid added slowly accompanied by stirring.
0.4 I distilled wash water was added. This solution is termed acid solution.
The basic solution was introduced into the laboratory autoclave (capacity: 4 litres) at 600 rpm stirrer speed, the autoclave loaded with approx. 6 - 7 bar nitrogen via the dipping tube and relieved again via the vent valve. The procedure was repeated three times.
A disperser (IKA, ULTRATURRAX0 UTL 25 Basic Inline with dispersion chamber DK 25.11) was connected to the autoclave between vent valve and bottom outlet valve in order to carry out the dispersion or grinding treatment. The pumping direction of the disperser was bottom outlet valve - disperser - vent valve. The disperser was started on the middle power level (13,500 rpm) according to the manufacturer's instructions.
The prepared acid solution was then pumped with a membrane 5 pump via the dipping tube into the autoclave (stroke 100%, 180 strokes/minute; corresponds to the maximum capacity of the pump) and reflushed with approx. 500 to 600 ml distilled water. The pumping-in lasted for approx. 20 minutes, wherein the temperature of the resultant suspension increased to 10 approx. 40 C. After pumping-in of the acid solution, a deposit precipitated out.
The disperser, which was started before the addition of the acid solution, was used for a total of approx. 1 hour for 15 intensive mixing or grinding of the resultant, viscous suspension (after pumping-in of the acid solution at 50 C) The use of a disperser brings an intensive mixing and the agglomeration of the precipitated viscous pre-mixture. During 20 the precipitation and crystallization of the suspension, a homogeneous mixture of many small, approximately equally-sized crystal nuclei formed in the disperser as a result of the pre-grinding or intensive mixing. These crystal nuclei crystallized during the subsequent hydrothermal treatment (see below) to very uniformly grown crystals of the end-product with a very narrow particle-size distribution. The power and energy input via the dispersion treatment was respectively more than 7 kW/m3 and more than 7 kWh/m3 of the treated precursor mixture/suspension.
Hydrothermal treatment Each freshly produced suspension was subjected to hydrothermal treatment in the laboratory autoclave. Before heating the suspension, the autoclave was flushed with nitrogen in order to expel any air present from the autoclave before the hydrothermal process. The product according to the invention formed starting from hydrothermal temperatures of approximately 100 to 120 C. The hydrothermal treatment was preferably carried out for 2 hours at 130 C.
After switching off and disconnecting the disperser the mixture was heated over 1.5 hours to 130 C, for 2 hours.
Cooling to 30 C then took place over 3 hours.
LiMn0.56Feo.33Zn0.1cPO4 was then dried in air or in the drying oven for example at mild temperatures (40 C) without visible oxidation. The atomic ratio Li/Y
, ¨Fe + Mn + M was 0.85 indicating a lithium deficiency.
The thus-obtained material was pumped under nitrogen atmosphere through the bottom outlet valve of the autoclave into a pressure filter (Seitz filter). The membrane pump setting was such that a pressure of 5 bar was not exceeded.
The filter cake was subsequently washed with distilled water until the conductivity of the wash water had fallen below 42 pS/cm.
Comparative Example 2:
Synthesis of LiMn0.56Feo.33Mgo.10PO4 The synthesis was carried out as in Example 1, except that 20.80 g MgSO4*7 H20 was used as starting material in the corresponding molar weight quantities instead of ZnSO4. The atomic ratio Liae+m, +14 was 0.87 indicating a lithium deficiency.
Comparative Example 3:
Synthesis of LiMn0.80Feo1oZn0.10PO4 The synthesis was carried out as in Example 1, except that 114.12 g MnSO4*1 H20, 23.46 g FeSO4*7 H20, 24.27 g ZnSO4*7 H20, 103.38 g HPO4, (80%) were used as starting materials in the corresponding molar weight quantities. The atomic ratio Liapc+
fm was 0.78 indicating a lithium deficiency.
Comparative Example 4:
Synthesis of LiMn0.85Fe0.1oZn0.o5PO4 The synthesis was carried out as in Example 1, except that 121.26 g MnSO4*1 H20, 23.46 g FeSO4*7 H20, 12.14 g ZnSO4*7 E120, 103.38 g H3PO4 (80%) were used as starting materials in the corresponding molar weight quantities. The atomic ratio Li/EFe+
m, +1,1 was 0.82 indicating a lithium deficiency.
Example /:
Synthesis of Li0.99Mn0.56Fe0.33Zn0.10PO4(304) 0.006 The synthesis was carried out according to comparative example 1 with the difference that additionally 100 ml of a 0.1 m solution of Li2SO4 was added to the starting materials to obtain the desired stoichiometry. The atomic ratio Li/Epe + Mn + m was 0.99 indicating no lithium deficiency.
Example 2:
Synthesis of Iii0.9914.n0.56Fe0.33Zn0.10PO4 (504) The synthesis was carried out according to comparative example 1 with the difference that additionally 100 ml of a 0.1 m solution of Li2SO4 was added to the starting materials to obtain the desired stoichiometry. The atomic ratio Li/E+, Mn + m was 0.99 indicating no lithium deficiency.
Example 3:
The following materials (with the atomic ratio Li/E, Mn + m determined by ICP-OES measurements (Varian Vista Pro 720 ES) were synthesized according to example 1 but varying the amounts of the lithium sulphate solution.
LiMno.56Fe0.33ZnJ.10PO4 (SO4) 0.01 (atomic ratio Li/+e 0 .
937) , Li,<Mn0.59Fe0.34Zni.0 ,PO4 (SO4) ( (atomic ratio Li/+e + Mn + m:
0. 911) ;
LiõMn0.80Fe0.1Zno.c5PO4 (SO4) o.oi (atomic ratio Li/E++ + Mi + m: 0.930) ;
Li.Mn0.6iFeo.34Zno.o5PO4(SO4)0.01 (atomic ratio L1/Fe + Mn + Iv_: 0.964) Li,Mn0.63Fe0.34Zni.09PO4 (SO4) o.qi (atomic ratio Li/4 A + Mn + M: 0 . 972) ;
LixMn0.59Feo.34Zno.c7PO4 (SO4) u. )u6 (atomic ratio Li/Ere + Mn + m: 0. 945);
LixMno.80Fem.15Zni.m5PO4(SO4) O. 006 (atomic ratio Li/+e + Mn +M: 0 . 973);
LixlvIno.61Fe0.34Zno.05PO4 (SO4) 0.006 (atomic ratio Li /Y
, ¨Fe + Mn +M
0.981) LixMn0.63Fe0.34Zno.03PO4 (SO4) 0.006 (atomic ratio L i /Epc + + m :
0 . 922) Example 4:
Carbon coating of the obtained materials (variant I) The filter cakes obtained in Examples 1 to 4 were impregnated with a solution of 24 g lactose in water and then calcined at 750 C for 3 hours under nitrogen.
Depending on the quantity of lactose, the proportion of carbon in the product according to the invention was between 0.2 and 4 wt.-%.
Typically 1 kg dry product from Examples 1 and 2 was mixed intimately with 112 g lactose monohydrate and 330 g deionized water and dried overnight in a vacuum drying oven at 105 C and < 100 mbar to a residual moisture of 3%. The brittle drying product was broken by hand and coarse-ground in a disk mill (Fritsch Pulverisette 13) with a 1 mm space between disks and transferred in high-grade steel cups into a protective gas chamber furnace (Linn KS 80-S). The latter was heated to 750 C
within 3 hours at a nitrogen stream of 200 l/h, kept at this temperature for 3 hours and cooled over 3 hours to room temperature. The carbon-containing product was disagglomerated in a jet mill (Hosokawa).
The SEM analysis of the particle-size distribution produced the following values: D51 < 0.5 pm, difference between Dn and Dic, value: < 1 pm.
Example 5:
Carbon coating of the obtained materials (variant 2) The synthesis of the materials according to the invention was carried out as in Examples 1 to 4, except that gelatine was also then added (9 g gelatine per 100 g starting product) during the precipitation step a). The end-product contained approx. 2.3 wt.-% carbon.
Example 6: Manufacture of electrodes Thin-film electrodes as disclosed for example in Anderson et al., Electrochem. and Solid State Letters 3 (2) 2000, pages 66-68 were produced. The electrode compositions usually consisted of 90 parts by weight active material, 5 parts by 10 weight Super P carbon and 5-% polyvinylidene fluoride as binder or 80 parts by weight active material, 15 wt.-% Super P
carbon and 5 parts by weight polyvinylidene fluoride, or 95 parts by weight active material and 5 parts by weight polyvinylidene fluoride.
The active material was mixed, together with the binder (or, for the electrodes of the state of the art, with the added conductive agent), in N-methylpyrrolidone, applied to a pretreated (primer) aluminium foil by means of a doctor blade and the N-methylpyrrolidone was evaporated at 105 C under vacuum. The electrodes were then cut out (13 mm diameter) and roll-coated with a roller at room temperature. The starting nip width was e.g. 0.1 mm and the desired electrode thickness progressively adjusted in steps of 5-10 pm. 4 rolled coats were applied at each step and the foil was rotated by 180 .
After this treatment, the thickness of the coating was between 20-25pm. The primer on the aluminium foil consisted of a thin carbon coating which improves the adhesion of the active material particularly when the active material content of the electrode is more than 85 wt.-%.
The electrodes were then dried overnight at 120 C under vacuum. Half cells were assembled in an argon-filled glovebox and were subsequently electrochemically measured..
The electrochemical measurements were carried out against lithium metal and using LP30 (Merck, Darmstadt) as electrolyte (EC (ethylene carbonate):DMC (dimethylcarbonate) = 1:1, 1 M
LiPF6)=
The charge procedure was carried out in CCCV mode, i.e. cycles with a constant current at the C/10 rate followed by a constant voltage portion at the voltage limits (4.3 volt versus Li/Li-') until the current fell approximately to the C/100 rate, in order to complete the charge.
Corresponding measurements of the specific capacity and the current carrying capacity were carried out on both Lix(Mn0.66Feo.33)PO4 of the state of the art and materials according to the invention substituted with magnesium and zinc.
Figure 1 shows the discharge curves at 1C and at room temperature for an electrode containing Li0.80Mnc.56Fe0A3Zno.loPO4 (Comparative Example 1) as active material. The ratio WEE, +mi, _1.4 was 0.8 which is an indicator for Li deficiency. The specific energy was measured to 446 mWh/g, the press density 1.51 g/cm3 and the volumetric energy 673 mWh/cm3. After several cycles, aloss of specific capacity was recorded in the range of 15 to 40 mAh/g.
Figure 2 shows the discharge curves at 1C and at room temperature for an electrode containing Li9A9Mn0.56Fe0.33Zn0.10PO4(SO4)0.006 (Example 1)as active material and Figure 3 the discharge curves at 1C and at room temperature for an electrode containing Li0A9Mn0.56Fe0.33Zn0.10PO4(SO4)0.01 (Example 2) as active material.
Compared to the material shown in Figure 1 representing state of the art the energy loss upon cycling is remarkably diminished. Both samples show basically no Li deficiency (Example 1 and Example 2 both have a Liape+ Mn +m ratio of 0.99. The specific energy for the electrode with Li0.99Mn0.56Fe0.33Zn0.10PO4(SO4)0A06as active material was measured as 522 mWh/g for the electrode with Li4.99M1-10.56Fe0.33Zno.10PO4(SO4)0.01 as active material to 527 mWH/g, i.e. remarkably higher than with the electrode of the prior art shown in figure 1. The same improvement was observed for the press density (1.86 g/cm3 and 2.15 g/cm3 respectively) and the volumetric energy (970 mWh/cm3 and 1133 mWh/cm3 respectively).
Figure 4 shows the discharge curves at 10 at room temperature for an electrode with Lio BoMn0.59Fei.34Zno.07PO4 as active material and in comparison Figure 5 the discharge curves at 10 at room temperature for an electrode containing Li0.91Mn0.59Fe0.34Zn007PO4(SO4)0.01 as active material. After several cycles it was observed that the energy loss upon cycling is remarkably diminished for the material Li991Mn0.59Fe034Zn007PO4(SO4)0.01 according to the invention compared to the prior art material LiMn0.59Fe0.14Zno.07PO4. The values for specific energy were determined as 525 mWH/g to 595 mWH/g showing the better performance of the material according to the invention. The same observation was made for the parameters press density (1.63 g/cm to 1.64 g/cm') and volumetric energy (855 mWh/cm' to 975 mWh/cm3).
Comparing the physical appearance (SEM images) of the particles of Li0.80Mn0.59Fe0.34Zn007PO4 in figure 6 with Li9A1Mn0.59Fe0.34Zn0.07PO4(SO4)oA1 in figure 7 it was observed that the particles of Lio.9114n4.59Fe0.34Zn0.07PO4(504)D.01 are slightly more finely grained and have a more regular shape than those of LiMn0.59Fe0.34Zn0.07PO4=
Figure 8 shows the discharge curves at 1C at room temperature for an electrode containing Li0.80Mho.e0Fee.1.,Zno.o5PO4 as active material and in comparison in figure 9 the discharge curves at 1C at room temperature for an electrode containing Li0.93Mno.80Fec.15Zno.05PO4(SO4)001 as active material. The same trend as observed beforehand was also observed for this material:
The values for specific energy were determined as 437 mWH/g to 575 mWH/g showing the better performance of the material according to the invention. The same observation was made for the parameters press density (1.70 g/cm3 to 1.72 g/cm3) and volumetric energy (751 mWh/cm3 to 978 mWh/cm3). The SEM images for both products are shown in figure 10 (Li0.80Mn0A0Feo.15Zno.05PO4) and figure 11 (LiMn0.80Fe0.15Zno.o5PO4(SO4)o.o1) with the same conclusion as beforehand.
Figure 12 shows the discharge curves at 1C at room temperature for an electrode containing LiMno olFe0.34Zni.05PO4 as active material and in comparison in figure 13 the discharge curves at 1C at room temperature for an electrode containing Li1.96Mno.6 FecA4Znon5PO4(SO4)0.21 as active material. The same trend as observed beforehand was also observed for this material:
The values for the specific energy were determined as 446 mWH/g to 595 mWH/g showing the better performance of the material according to the invention. The same observation was made for the volumetric energy (856 mWh/cm3 to 1011 mWh/cm3)whereas the press density (1.92 g/cm3 to 1.70 g/cm3) showed an inverse effect compared to the other materials discussed beforehand. The SEM images for both products are shown in figure 14 (Li0.80Mn3.61Fec.34Zno.05PO4) and figure 15 (Li0.96Mn0.61Fe0.34Zn0.05PO4(SO4)0.01) with the same conclusion as above.
Figure 16 shows the discharge curves at 10 at room temperature for an electrode containing Li0A0Mn0.63Fe034Zn0.03PO4 as active material and in comparison in figure 17 the discharge curves at 10 at room temperature for an electrode containing LijA7Mn0.63Fe034Zn003PO4(SO4)0.01 as active material. The same trend as observed beforehand was also observed for this material:
The values for the specific energy were determined as 436 mWH/g to 575 mWH/g showing the better performance of the material according to the invention. The same observation was made for the volumetric energy (785 mWh/cm3 to 1040 mWh/cm3)and the press density (1.80 g/cm3 to 1.81 g/cm3).
Examples 1. Determination of the particle-size distribution:
The particle-size distributions for the mixtures or suspensions and of the produced material is determined using the light scattering method using commercially available devices. This method is known per se to a person skilled in the art, wherein reference is also made in particular to the disclosure in JP 2002-151082 and WO 02/083555. In this case, the particle-size distributions were determined by a laser diffraction measurement apparatus (Mastersizer S. Malvern Instruments GmbH, Herrenberg, DE) and the manufacturer's software (version 2.19) with a Malvern Small Volume Sample Dispersion Unit, DIF 2002 as measuring unit. The following measuring conditions were selected: compressed range; active beam length 2.4 mm; measuring range: 300 RF; 0.05 to 900 pm.
The sample preparation and measurement took place according to the manufacturer's instructions.
The D(,0 value gives the value at which 90% of the particles in the measured sample have a smaller or the same particle diameter. Accordingly, the D50 value and the D10 value give the value at which 50% and 10% respectively of the particles in the measured sample have a smaller or the same particle diameter.
According to an embodiment according to the invention, the values mentioned in the present description are valid for the DK values, D50 values, the D90 values as well as the difference between the D90 and DK values relative to the volume proportion of the respective particles in the total volume. Accordingly, the DK, D50 and Dn values mentioned herein give the values at which 10 volume-% and 50 volume-% and 90 volume-% respectively of the particles in the measured sample have a smaller or the same particle diameter. If these values are obtained, particularly advantageous materials are provided according to the invention and negative influences of relatively coarse particles (with relatively larger volume proportion) on the processability and the electrochemical product properties are avoided. Preferably, the values mentioned in the present description are valid for the D10 values, the D50 values, the D90 values as well as the difference between the D90 and the D10 values relative to both percentage and volume percent of the particles.
For compositions (e.g. electrode materials) which, in addition to the lithium-manganese iron phosphates according to the invention are further doped with metal cations, contain further components, in particular for carbon-containing compositions, the above light scattering method can lead to misleading interpretations as the primary particles can form agglomerates within the suspension. However, the primary particle-size distribution of the material according to the invention can be directly determined as follows for such compositions using SEM photographs:
A small quantity of the powder sample is suspended in acetone and dispersed with ultrasound for 10 minutes. Immediately thereafter, a few drops of the suspension are dropped onto a sample plate of a scanning electron microscope (SEM). The solids concentration of the suspension and the number of drops are measured so that a large single-ply layer of powder particles forms on the support in order to prevent the powder particles from obscuring one another. The drops must be added rapidly before the particles can separate by size as a result of sedimentation. After drying in air, the sample is placed in the measuring chamber of the SEM. In the present example, this is a LEO 1530 apparatus which is operated with a field emission electrode at 1.5 kV excitation voltage and a 4 mm space between samples. At least 20 random sectional magnifications of the sample with a magnification factor of 20,000 are photographed. These are each printed on a DIN A4 sheet together with the inserted magnification scale. On each of the at least 20 sheets, if possible at least 10 free visible particles of the material according to the invention, from which the powder particles are formed together with the carbon-containing material, are randomly selected, wherein the boundaries of the particles of the material according to the invention are defined by the absence of fixed, direct connecting bridges. On the other hand, bridges formed by carbon material are included in the particle boundary. Of each of these selected particles, those with the longest and shortest axis in the projection are measured in each case with a ruler and converted to the actual particle dimensions using the scale ratio. For each measured particle, the arithmetic mean from the longest and the shortest axis is defined as particle diameter. The measured particles are then divided analogously to the light-scattering method into size classes.
The differential particle-size distribution relative to the number of particles is obtained by plotting the number of the associated particles in each case against the size class. The cumulative particle-size distribution from which Dlc, D50 and DK can be read directly on the size axis is obtained by continually totalling the particle numbers from the small to the large particle classes.
The described process was also applied to battery electrodes containing the material according to the invention. In this case, however, instead of a powder sample a fresh cut or fracture surface of the electrode is secured to the sample holder and examined under a SEM.
When producing the materials, it is to be borne in mind that the materials are precipitated from an aqueous Fe precursor solution. The reaction and drying/sintering is therefore preferably to be carried out under protective gas or vacuum in order to avoid a partial oxidation of Fe2+ to Fe '+ with formation of by-products such as Fe2O3 or FePO4.
Comparative Example 1:
Synthesis of Li0A0Mn0.56Fe0.33Zn0.10PO4 Production and precipitation/suspension of a precursor mixture First, 105.5 g lithium hydroxide LiOH = H20 was dissolved in 0.9 I distilled water. This solution is called basic solution.
77.43 g FeSO4 x 7 H20, 79.88 g MnSO4x H20 and 24.27 g ZnSO4 x 7 H20 were dissolved in approx. 1.5 I distilled water and 103.38 g 80-% phosphoric acid added slowly accompanied by stirring.
0.4 I distilled wash water was added. This solution is termed acid solution.
The basic solution was introduced into the laboratory autoclave (capacity: 4 litres) at 600 rpm stirrer speed, the autoclave loaded with approx. 6 - 7 bar nitrogen via the dipping tube and relieved again via the vent valve. The procedure was repeated three times.
A disperser (IKA, ULTRATURRAX0 UTL 25 Basic Inline with dispersion chamber DK 25.11) was connected to the autoclave between vent valve and bottom outlet valve in order to carry out the dispersion or grinding treatment. The pumping direction of the disperser was bottom outlet valve - disperser - vent valve. The disperser was started on the middle power level (13,500 rpm) according to the manufacturer's instructions.
The prepared acid solution was then pumped with a membrane 5 pump via the dipping tube into the autoclave (stroke 100%, 180 strokes/minute; corresponds to the maximum capacity of the pump) and reflushed with approx. 500 to 600 ml distilled water. The pumping-in lasted for approx. 20 minutes, wherein the temperature of the resultant suspension increased to 10 approx. 40 C. After pumping-in of the acid solution, a deposit precipitated out.
The disperser, which was started before the addition of the acid solution, was used for a total of approx. 1 hour for 15 intensive mixing or grinding of the resultant, viscous suspension (after pumping-in of the acid solution at 50 C) The use of a disperser brings an intensive mixing and the agglomeration of the precipitated viscous pre-mixture. During 20 the precipitation and crystallization of the suspension, a homogeneous mixture of many small, approximately equally-sized crystal nuclei formed in the disperser as a result of the pre-grinding or intensive mixing. These crystal nuclei crystallized during the subsequent hydrothermal treatment (see below) to very uniformly grown crystals of the end-product with a very narrow particle-size distribution. The power and energy input via the dispersion treatment was respectively more than 7 kW/m3 and more than 7 kWh/m3 of the treated precursor mixture/suspension.
Hydrothermal treatment Each freshly produced suspension was subjected to hydrothermal treatment in the laboratory autoclave. Before heating the suspension, the autoclave was flushed with nitrogen in order to expel any air present from the autoclave before the hydrothermal process. The product according to the invention formed starting from hydrothermal temperatures of approximately 100 to 120 C. The hydrothermal treatment was preferably carried out for 2 hours at 130 C.
After switching off and disconnecting the disperser the mixture was heated over 1.5 hours to 130 C, for 2 hours.
Cooling to 30 C then took place over 3 hours.
LiMn0.56Feo.33Zn0.1cPO4 was then dried in air or in the drying oven for example at mild temperatures (40 C) without visible oxidation. The atomic ratio Li/Y
, ¨Fe + Mn + M was 0.85 indicating a lithium deficiency.
The thus-obtained material was pumped under nitrogen atmosphere through the bottom outlet valve of the autoclave into a pressure filter (Seitz filter). The membrane pump setting was such that a pressure of 5 bar was not exceeded.
The filter cake was subsequently washed with distilled water until the conductivity of the wash water had fallen below 42 pS/cm.
Comparative Example 2:
Synthesis of LiMn0.56Feo.33Mgo.10PO4 The synthesis was carried out as in Example 1, except that 20.80 g MgSO4*7 H20 was used as starting material in the corresponding molar weight quantities instead of ZnSO4. The atomic ratio Liae+m, +14 was 0.87 indicating a lithium deficiency.
Comparative Example 3:
Synthesis of LiMn0.80Feo1oZn0.10PO4 The synthesis was carried out as in Example 1, except that 114.12 g MnSO4*1 H20, 23.46 g FeSO4*7 H20, 24.27 g ZnSO4*7 H20, 103.38 g HPO4, (80%) were used as starting materials in the corresponding molar weight quantities. The atomic ratio Liapc+
fm was 0.78 indicating a lithium deficiency.
Comparative Example 4:
Synthesis of LiMn0.85Fe0.1oZn0.o5PO4 The synthesis was carried out as in Example 1, except that 121.26 g MnSO4*1 H20, 23.46 g FeSO4*7 H20, 12.14 g ZnSO4*7 E120, 103.38 g H3PO4 (80%) were used as starting materials in the corresponding molar weight quantities. The atomic ratio Li/EFe+
m, +1,1 was 0.82 indicating a lithium deficiency.
Example /:
Synthesis of Li0.99Mn0.56Fe0.33Zn0.10PO4(304) 0.006 The synthesis was carried out according to comparative example 1 with the difference that additionally 100 ml of a 0.1 m solution of Li2SO4 was added to the starting materials to obtain the desired stoichiometry. The atomic ratio Li/Epe + Mn + m was 0.99 indicating no lithium deficiency.
Example 2:
Synthesis of Iii0.9914.n0.56Fe0.33Zn0.10PO4 (504) The synthesis was carried out according to comparative example 1 with the difference that additionally 100 ml of a 0.1 m solution of Li2SO4 was added to the starting materials to obtain the desired stoichiometry. The atomic ratio Li/E+, Mn + m was 0.99 indicating no lithium deficiency.
Example 3:
The following materials (with the atomic ratio Li/E, Mn + m determined by ICP-OES measurements (Varian Vista Pro 720 ES) were synthesized according to example 1 but varying the amounts of the lithium sulphate solution.
LiMno.56Fe0.33ZnJ.10PO4 (SO4) 0.01 (atomic ratio Li/+e 0 .
937) , Li,<Mn0.59Fe0.34Zni.0 ,PO4 (SO4) ( (atomic ratio Li/+e + Mn + m:
0. 911) ;
LiõMn0.80Fe0.1Zno.c5PO4 (SO4) o.oi (atomic ratio Li/E++ + Mi + m: 0.930) ;
Li.Mn0.6iFeo.34Zno.o5PO4(SO4)0.01 (atomic ratio L1/Fe + Mn + Iv_: 0.964) Li,Mn0.63Fe0.34Zni.09PO4 (SO4) o.qi (atomic ratio Li/4 A + Mn + M: 0 . 972) ;
LixMn0.59Feo.34Zno.c7PO4 (SO4) u. )u6 (atomic ratio Li/Ere + Mn + m: 0. 945);
LixMno.80Fem.15Zni.m5PO4(SO4) O. 006 (atomic ratio Li/+e + Mn +M: 0 . 973);
LixlvIno.61Fe0.34Zno.05PO4 (SO4) 0.006 (atomic ratio Li /Y
, ¨Fe + Mn +M
0.981) LixMn0.63Fe0.34Zno.03PO4 (SO4) 0.006 (atomic ratio L i /Epc + + m :
0 . 922) Example 4:
Carbon coating of the obtained materials (variant I) The filter cakes obtained in Examples 1 to 4 were impregnated with a solution of 24 g lactose in water and then calcined at 750 C for 3 hours under nitrogen.
Depending on the quantity of lactose, the proportion of carbon in the product according to the invention was between 0.2 and 4 wt.-%.
Typically 1 kg dry product from Examples 1 and 2 was mixed intimately with 112 g lactose monohydrate and 330 g deionized water and dried overnight in a vacuum drying oven at 105 C and < 100 mbar to a residual moisture of 3%. The brittle drying product was broken by hand and coarse-ground in a disk mill (Fritsch Pulverisette 13) with a 1 mm space between disks and transferred in high-grade steel cups into a protective gas chamber furnace (Linn KS 80-S). The latter was heated to 750 C
within 3 hours at a nitrogen stream of 200 l/h, kept at this temperature for 3 hours and cooled over 3 hours to room temperature. The carbon-containing product was disagglomerated in a jet mill (Hosokawa).
The SEM analysis of the particle-size distribution produced the following values: D51 < 0.5 pm, difference between Dn and Dic, value: < 1 pm.
Example 5:
Carbon coating of the obtained materials (variant 2) The synthesis of the materials according to the invention was carried out as in Examples 1 to 4, except that gelatine was also then added (9 g gelatine per 100 g starting product) during the precipitation step a). The end-product contained approx. 2.3 wt.-% carbon.
Example 6: Manufacture of electrodes Thin-film electrodes as disclosed for example in Anderson et al., Electrochem. and Solid State Letters 3 (2) 2000, pages 66-68 were produced. The electrode compositions usually consisted of 90 parts by weight active material, 5 parts by 10 weight Super P carbon and 5-% polyvinylidene fluoride as binder or 80 parts by weight active material, 15 wt.-% Super P
carbon and 5 parts by weight polyvinylidene fluoride, or 95 parts by weight active material and 5 parts by weight polyvinylidene fluoride.
The active material was mixed, together with the binder (or, for the electrodes of the state of the art, with the added conductive agent), in N-methylpyrrolidone, applied to a pretreated (primer) aluminium foil by means of a doctor blade and the N-methylpyrrolidone was evaporated at 105 C under vacuum. The electrodes were then cut out (13 mm diameter) and roll-coated with a roller at room temperature. The starting nip width was e.g. 0.1 mm and the desired electrode thickness progressively adjusted in steps of 5-10 pm. 4 rolled coats were applied at each step and the foil was rotated by 180 .
After this treatment, the thickness of the coating was between 20-25pm. The primer on the aluminium foil consisted of a thin carbon coating which improves the adhesion of the active material particularly when the active material content of the electrode is more than 85 wt.-%.
The electrodes were then dried overnight at 120 C under vacuum. Half cells were assembled in an argon-filled glovebox and were subsequently electrochemically measured..
The electrochemical measurements were carried out against lithium metal and using LP30 (Merck, Darmstadt) as electrolyte (EC (ethylene carbonate):DMC (dimethylcarbonate) = 1:1, 1 M
LiPF6)=
The charge procedure was carried out in CCCV mode, i.e. cycles with a constant current at the C/10 rate followed by a constant voltage portion at the voltage limits (4.3 volt versus Li/Li-') until the current fell approximately to the C/100 rate, in order to complete the charge.
Corresponding measurements of the specific capacity and the current carrying capacity were carried out on both Lix(Mn0.66Feo.33)PO4 of the state of the art and materials according to the invention substituted with magnesium and zinc.
Figure 1 shows the discharge curves at 1C and at room temperature for an electrode containing Li0.80Mnc.56Fe0A3Zno.loPO4 (Comparative Example 1) as active material. The ratio WEE, +mi, _1.4 was 0.8 which is an indicator for Li deficiency. The specific energy was measured to 446 mWh/g, the press density 1.51 g/cm3 and the volumetric energy 673 mWh/cm3. After several cycles, aloss of specific capacity was recorded in the range of 15 to 40 mAh/g.
Figure 2 shows the discharge curves at 1C and at room temperature for an electrode containing Li9A9Mn0.56Fe0.33Zn0.10PO4(SO4)0.006 (Example 1)as active material and Figure 3 the discharge curves at 1C and at room temperature for an electrode containing Li0A9Mn0.56Fe0.33Zn0.10PO4(SO4)0.01 (Example 2) as active material.
Compared to the material shown in Figure 1 representing state of the art the energy loss upon cycling is remarkably diminished. Both samples show basically no Li deficiency (Example 1 and Example 2 both have a Liape+ Mn +m ratio of 0.99. The specific energy for the electrode with Li0.99Mn0.56Fe0.33Zn0.10PO4(SO4)0A06as active material was measured as 522 mWh/g for the electrode with Li4.99M1-10.56Fe0.33Zno.10PO4(SO4)0.01 as active material to 527 mWH/g, i.e. remarkably higher than with the electrode of the prior art shown in figure 1. The same improvement was observed for the press density (1.86 g/cm3 and 2.15 g/cm3 respectively) and the volumetric energy (970 mWh/cm3 and 1133 mWh/cm3 respectively).
Figure 4 shows the discharge curves at 10 at room temperature for an electrode with Lio BoMn0.59Fei.34Zno.07PO4 as active material and in comparison Figure 5 the discharge curves at 10 at room temperature for an electrode containing Li0.91Mn0.59Fe0.34Zn007PO4(SO4)0.01 as active material. After several cycles it was observed that the energy loss upon cycling is remarkably diminished for the material Li991Mn0.59Fe034Zn007PO4(SO4)0.01 according to the invention compared to the prior art material LiMn0.59Fe0.14Zno.07PO4. The values for specific energy were determined as 525 mWH/g to 595 mWH/g showing the better performance of the material according to the invention. The same observation was made for the parameters press density (1.63 g/cm to 1.64 g/cm') and volumetric energy (855 mWh/cm' to 975 mWh/cm3).
Comparing the physical appearance (SEM images) of the particles of Li0.80Mn0.59Fe0.34Zn007PO4 in figure 6 with Li9A1Mn0.59Fe0.34Zn0.07PO4(SO4)oA1 in figure 7 it was observed that the particles of Lio.9114n4.59Fe0.34Zn0.07PO4(504)D.01 are slightly more finely grained and have a more regular shape than those of LiMn0.59Fe0.34Zn0.07PO4=
Figure 8 shows the discharge curves at 1C at room temperature for an electrode containing Li0.80Mho.e0Fee.1.,Zno.o5PO4 as active material and in comparison in figure 9 the discharge curves at 1C at room temperature for an electrode containing Li0.93Mno.80Fec.15Zno.05PO4(SO4)001 as active material. The same trend as observed beforehand was also observed for this material:
The values for specific energy were determined as 437 mWH/g to 575 mWH/g showing the better performance of the material according to the invention. The same observation was made for the parameters press density (1.70 g/cm3 to 1.72 g/cm3) and volumetric energy (751 mWh/cm3 to 978 mWh/cm3). The SEM images for both products are shown in figure 10 (Li0.80Mn0A0Feo.15Zno.05PO4) and figure 11 (LiMn0.80Fe0.15Zno.o5PO4(SO4)o.o1) with the same conclusion as beforehand.
Figure 12 shows the discharge curves at 1C at room temperature for an electrode containing LiMno olFe0.34Zni.05PO4 as active material and in comparison in figure 13 the discharge curves at 1C at room temperature for an electrode containing Li1.96Mno.6 FecA4Znon5PO4(SO4)0.21 as active material. The same trend as observed beforehand was also observed for this material:
The values for the specific energy were determined as 446 mWH/g to 595 mWH/g showing the better performance of the material according to the invention. The same observation was made for the volumetric energy (856 mWh/cm3 to 1011 mWh/cm3)whereas the press density (1.92 g/cm3 to 1.70 g/cm3) showed an inverse effect compared to the other materials discussed beforehand. The SEM images for both products are shown in figure 14 (Li0.80Mn3.61Fec.34Zno.05PO4) and figure 15 (Li0.96Mn0.61Fe0.34Zn0.05PO4(SO4)0.01) with the same conclusion as above.
Figure 16 shows the discharge curves at 10 at room temperature for an electrode containing Li0A0Mn0.63Fe034Zn0.03PO4 as active material and in comparison in figure 17 the discharge curves at 10 at room temperature for an electrode containing LijA7Mn0.63Fe034Zn003PO4(SO4)0.01 as active material. The same trend as observed beforehand was also observed for this material:
The values for the specific energy were determined as 436 mWH/g to 575 mWH/g showing the better performance of the material according to the invention. The same observation was made for the volumetric energy (785 mWh/cm3 to 1040 mWh/cm3)and the press density (1.80 g/cm3 to 1.81 g/cm3).
Claims (14)
1. Mixed lithium-manganese-metal phosphate of formula Li x Fe y Mn1-y M1- (y+z) (PO4) u (SO4) v wherein M is a metal selected from the group Co, Ni, Al, Mg, Sn, Pb, Nb, B, Cu, Cr, Mo, Ru, V, Ga, Ca, Sr, Ba, Ti, Zr, Cd and mixtures thereof and wherein:
0.9 <=x 1.5, 0 <=y < 1, and 0.001 <=(y + z)<= 1 and 0.75 < u < 1.0 and 0 < v<= 0.25.
0.9 <=x 1.5, 0 <=y < 1, and 0.001 <=(y + z)<= 1 and 0.75 < u < 1.0 and 0 < v<= 0.25.
2. Mixed lithium-manganese-metal phosphate according to claim 1, wherein M is selected from Co, Mg, Nb, Ni, Al, Zn and mixtures thereof.
3. Mixed lithium-manganese-metal phosphate according to claim 2, wherein M is Zn or Mg or mixtures thereof.
4.
Mixed lithium-manganese-metal phosphate according to any one of claims 1 to 3, wherein the atomic ratio Li/7/.SIGMA.Fe + Mn + M is in the range between 0.9 to 1.5.
Mixed lithium-manganese-metal phosphate according to any one of claims 1 to 3, wherein the atomic ratio Li/7/.SIGMA.Fe + Mn + M is in the range between 0.9 to 1.5.
5.
Mixed lithium-manganese-metal phosphate according to any one of claims 1 to 4, further comprising carbon.
Mixed lithium-manganese-metal phosphate according to any one of claims 1 to 4, further comprising carbon.
6. Mixed lithium-manganese-metal phosphate according to claim 5, wherein carbon is evenly distributed throughout the mixed lithium-manganese-metal phosphate and/or the individual particles of the mixed lithium-manganese-metal phosphate are partially or entirely coated with carbon.
7. Mixed lithium-manganese-metal phosphate according to claim 5 or 6, wherein the amount of carbon relative to the substituted mixed lithium-manganese-metal phosphate is <=4 wt.-%.
8.
Cathode for a secondary lithium-ion battery containing a mixed lithium-manganese-metal phosphate according to any one of claims 1 to 7.
Cathode for a secondary lithium-ion battery containing a mixed lithium-manganese-metal phosphate according to any one of claims 1 to 7.
9. Cathode according to claim 8, which is free of added conductive agents.
10. Process for producing a mixed lithium-manganese-metal phosphate according to any one of claims 1 to 7, comprising the following steps:
a. providing an aqueous mixture with a pH ( 7.5 containing at least one Li starting compound, one Mn starting compound, one Fe starting compound, optionally one M starting compound, one P043- and one SO4- starting compound until a precipitate or suspension forms, b. carrying out a dispersion or grinding treatment of the mixture and/or the suspension, c. obtaining the mixed lithium-manganese-metal phosphate, from the suspension by reaction of the suspension under hydrothermal conditions.
a. providing an aqueous mixture with a pH ( 7.5 containing at least one Li starting compound, one Mn starting compound, one Fe starting compound, optionally one M starting compound, one P043- and one SO4- starting compound until a precipitate or suspension forms, b. carrying out a dispersion or grinding treatment of the mixture and/or the suspension, c. obtaining the mixed lithium-manganese-metal phosphate, from the suspension by reaction of the suspension under hydrothermal conditions.
11. Process according to claim 10, wherein in step a) or step c) a further, carbon-containing, component is added.
12. Process according to claim 10, wherein the mixed lithium-manganese-metal phosphate obtained in step c) is mixed with a carbon-containing component.
13. Process according to any one of claims 10 to 12, wherein two different Li sources are used.
14. Process according to claim 13, wherein one Li source is Li2SO4.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP12180404.1 | 2012-08-14 | ||
| EP12180404.1A EP2698346A1 (en) | 2012-08-14 | 2012-08-14 | Mixed sulphate containing lithium-manganese-metal phosphate |
| PCT/EP2013/067038 WO2014027046A2 (en) | 2012-08-14 | 2013-08-14 | Mixed sulphate containing lithium-manganese-metal phosphate |
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| CA2877556C true CA2877556C (en) | 2020-10-06 |
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| CA2877556A Active CA2877556C (en) | 2012-08-14 | 2013-08-14 | Mixed sulphate containing lithium-manganese-metal phosphate |
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| US (1) | US20150232337A1 (en) |
| EP (2) | EP2698346A1 (en) |
| JP (1) | JP6574133B2 (en) |
| KR (1) | KR101751423B1 (en) |
| CN (1) | CN104603050B (en) |
| CA (1) | CA2877556C (en) |
| TW (1) | TW201431779A (en) |
| WO (1) | WO2014027046A2 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102220905B1 (en) * | 2016-09-23 | 2021-02-26 | 삼성에스디아이 주식회사 | Negative electrode active material for lithium secondary battery, and lithium secondary battery including negative electrode comprising the negative electrode active material |
| CN109987616B (en) * | 2019-05-08 | 2021-07-30 | 上海中锂实业有限公司 | A method for directly preparing battery-grade lithium hydroxide from lithium phosphate |
| CN110937641B (en) * | 2019-11-20 | 2022-02-08 | 哈尔滨工业大学（深圳） | Sn element doped cobalt-free manganese-based solid solution lithium ion battery anode material and preparation method thereof |
| CN113258073B (en) * | 2021-07-06 | 2021-09-28 | 湖南长远锂科股份有限公司 | Coating modified lithium ion battery anode material and preparation method thereof |
| CN114212764B (en) * | 2021-11-30 | 2023-06-30 | 厦门厦钨新能源材料股份有限公司 | Phosphate positive electrode material precursor, preparation method and application thereof |
| CN114348982A (en) * | 2022-01-10 | 2022-04-15 | 雅安天蓝新材料科技有限公司 | Ferrous manganous phosphate, ferrous manganous lithium phosphate, preparation methods thereof, lithium ion battery and electric equipment |
| CN116081589B (en) * | 2022-10-12 | 2024-03-29 | 北京钠谛科技有限公司 | Lithium-rich lithium iron manganese phosphate material and preparation method thereof |
| EP4693485A1 (en) * | 2023-04-13 | 2026-02-11 | Contemporary Amperex Technology Co., Limited | Positive electrode active material, positive electrode slurry, positive electrode sheet, battery, and electric device |
| CN117174898A (en) * | 2023-09-27 | 2023-12-05 | 惠州亿纬动力电池有限公司 | Lithium iron manganese phosphate material and its preparation method, positive electrode sheet and its preparation method, battery |
| CN117865108A (en) * | 2024-01-23 | 2024-04-12 | 天津大学 | Doped ferromanganese phosphate and preparation method thereof |
| WO2026009121A1 (en) * | 2024-07-05 | 2026-01-08 | 株式会社半導体エネルギー研究所 | Lithium-ion battery |
Family Cites Families (32)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5910382A (en) | 1996-04-23 | 1999-06-08 | Board Of Regents, University Of Texas Systems | Cathode materials for secondary (rechargeable) lithium batteries |
| US6514640B1 (en) | 1996-04-23 | 2003-02-04 | Board Of Regents, The University Of Texas System | Cathode materials for secondary (rechargeable) lithium batteries |
| CN1311808A (en) | 1998-05-29 | 2001-09-05 | 索罗蒂亚公司 | Nucleation of polyamides in the presence of hypotphosphite |
| JP4495336B2 (en) | 2000-11-10 | 2010-07-07 | 株式会社Kri | A method for producing lithium iron phosphate. |
| DE10117904B4 (en) | 2001-04-10 | 2012-11-15 | Zentrum für Sonnenenergie- und Wasserstoff-Forschung Baden-Württemberg Gemeinnützige Stiftung | Binary, ternary and quaternary lithium iron phosphates, process for their preparation and their use |
| JP3631202B2 (en) * | 2001-12-21 | 2005-03-23 | 三洋電機株式会社 | Non-aqueous electrolyte battery |
| JP4187524B2 (en) * | 2002-01-31 | 2008-11-26 | 日本化学工業株式会社 | Lithium iron phosphorus composite oxide carbon composite, method for producing the same, lithium secondary battery positive electrode active material, and lithium secondary battery |
| KR100449073B1 (en) * | 2002-10-15 | 2004-09-18 | 한국전자통신연구원 | Cathode material for lithium secondary batteries and method for manufacturing the Same |
| JP4260572B2 (en) * | 2003-07-29 | 2009-04-30 | 日本化学工業株式会社 | Method for producing lithium iron phosphorus composite oxide carbon composite containing Mn atom |
| DE10353266B4 (en) * | 2003-11-14 | 2013-02-21 | Süd-Chemie Ip Gmbh & Co. Kg | Lithium iron phosphate, process for its preparation and its use as electrode material |
| JP4794833B2 (en) * | 2004-07-21 | 2011-10-19 | 日本コークス工業株式会社 | Positive electrode material for lithium ion secondary battery, method for producing the same, and lithium ion secondary battery |
| DE102005012640B4 (en) | 2005-03-18 | 2015-02-05 | Süd-Chemie Ip Gmbh & Co. Kg | Circular process for the wet-chemical production of lithium metal phosphates |
| JP4525474B2 (en) * | 2005-06-06 | 2010-08-18 | 株式会社豊田中央研究所 | Active material for lithium secondary battery and method for producing the same, lithium secondary battery |
| CA2566906A1 (en) * | 2006-10-30 | 2008-04-30 | Nathalie Ravet | Carbon-coated lifepo4 storage and handling |
| CN102037601B (en) | 2007-07-12 | 2014-04-23 | A123系统公司 | Multifunctional mixed metal olivines for lithium ion batteries |
| DE102007033460A1 (en) | 2007-07-18 | 2009-01-22 | Süd-Chemie AG | Circular process for the production of barium sulfate and lithium metal phosphate compounds |
| JP5323410B2 (en) * | 2007-07-27 | 2013-10-23 | 日本化学工業株式会社 | Method for producing lithium iron phosphorus-based composite oxide carbon composite and method for producing coprecipitate containing lithium, iron and phosphorus |
| JP5245351B2 (en) * | 2007-10-19 | 2013-07-24 | 株式会社豊田中央研究所 | Active material for lithium secondary battery and lithium secondary battery |
| FR2932396A1 (en) * | 2008-06-11 | 2009-12-18 | Centre Nat Rech Scient | PROCESS FOR THE PREPARATION OF INORGANIC OXIDES BY SOLVOTHERMAL PATHWAY |
| JP5509598B2 (en) * | 2009-01-09 | 2014-06-04 | 住友大阪セメント株式会社 | Electrode material and method for producing the same, and electrode and battery |
| EP2448044B1 (en) * | 2009-06-24 | 2019-02-27 | GS Yuasa International Ltd. | Positive electrode active material for lithium secondary battery, and lithium secondary battery |
| DE102010006077B4 (en) | 2010-01-28 | 2014-12-11 | Süd-Chemie Ip Gmbh & Co. Kg | Substituted lithium manganese metal phosphate |
| WO2011100487A2 (en) * | 2010-02-12 | 2011-08-18 | Applied Materials, Inc. | HYDROTHERMAL SYNTHESIS OF LiFePO4 NANOPARTICLES |
| KR101810259B1 (en) * | 2010-03-19 | 2017-12-18 | 도다 고교 가부시끼가이샤 | Method for producing lithium manganese iron phosphate particulate powder, lithium manganese iron phosphate particulate powder and non-aqueous electrolyte secondary battery using that particulate powder |
| CN103109399B (en) * | 2010-09-10 | 2015-11-25 | 海洋王照明科技股份有限公司 | A kind of containing lithium salts-graphene composite material and preparation method thereof |
| CN101997118A (en) * | 2010-11-02 | 2011-03-30 | 天津斯特兰能源科技有限公司 | Lithium ferric manganese phosphate as cathode material of lithium ion battery and preparation method thereof |
| US20120138867A1 (en) * | 2010-11-11 | 2012-06-07 | Phostech Lithium Inc. | Carbon-deposited alkali metal oxyanion electrode material and process for preparing same |
| CN102290245B (en) * | 2011-04-29 | 2012-11-21 | 深圳市惠程电气股份有限公司 | Polyimide capacitor battery and manufacturing method thereof |
| CN102249208A (en) * | 2011-05-06 | 2011-11-23 | 朱鸥鹭 | Hydrothermal synthesis method for lithium ferromanganese phosphate anode material of lithium ion battery |
| EP2522625B1 (en) * | 2011-05-13 | 2014-06-04 | Shin-Etsu Chemical Co., Ltd. | Preparation of particulate positive electrode material for lithium ion cells |
| US20120328774A1 (en) * | 2011-06-22 | 2012-12-27 | Phostech Lithium Inc. | Carbon-deposited alkali metal oxyanion electrode material and process of preparing same |
| US8766697B2 (en) * | 2012-08-01 | 2014-07-01 | Stmicroelectronics International N.V. | Level shifting circuit with adaptive feedback |
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2012
- 2012-08-14 EP EP12180404.1A patent/EP2698346A1/en not_active Withdrawn
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2013
- 2013-08-14 TW TW102129079A patent/TW201431779A/en unknown
- 2013-08-14 US US14/421,576 patent/US20150232337A1/en not_active Abandoned
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- 2013-08-14 EP EP13748340.0A patent/EP2885247B1/en active Active
- 2013-08-14 WO PCT/EP2013/067038 patent/WO2014027046A2/en not_active Ceased
- 2013-08-14 JP JP2015526986A patent/JP6574133B2/en active Active
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| JP6574133B2 (en) | 2019-09-11 |
| TW201431779A (en) | 2014-08-16 |
| US20150232337A1 (en) | 2015-08-20 |
| EP2698346A1 (en) | 2014-02-19 |
| WO2014027046A2 (en) | 2014-02-20 |
| EP2885247A2 (en) | 2015-06-24 |
| KR20150042218A (en) | 2015-04-20 |
| WO2014027046A3 (en) | 2014-04-03 |
| CA2877556A1 (en) | 2014-02-20 |
| EP2885247B1 (en) | 2018-03-28 |
| JP2015526860A (en) | 2015-09-10 |
| CN104603050A (en) | 2015-05-06 |
| KR101751423B1 (en) | 2017-06-27 |
| CN104603050B (en) | 2017-09-08 |
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