# Patent

## Title
Nanoparticulate composition and method for its production

## Abstract

The present invention relates to a nanoparticulate composition comprising nanoparticles with a particle-size distribution of d90≦10 μm, and optionally a surface-active agent.
The present invention further relates to a method for the production of such a nanoparticulate composition.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This is a National Phase application of PCT application number PCT/EP2008/010399, filed Dec. 8, 2008, which claims priority benefit of German application number DE 10 2007 058 674.6, filed Dec. 6, 2007, the content of such applications being incorporated herein by reference.
FIELD OF THE INVENTION
The present invention relates to a nanoparticulate composition and methods for the production of same. The present invention also relates to the use of such nanoparticulate compositions for the production of battery materials.
BACKGROUND OF THE INVENTION
Nanoparticles, i.e. solids produced as powder or dispersed in liquid media, the individual particles of which extend typically less than 1000 nm in at least two dimensions and which are composed of chemical elements, inorganic or organic compounds or composites, have been used for several years for many applications.
For example, nanoparticles are used as catalyst starting substances, as nanoparticles often have a high BET surface area.
Typically, in what is called the wet-chemical synthesis of nanocrystalline powders or nanoparticles starting from so-called precursor compounds, a powder is synthesized by chemical reactions for example by means of precipitations or by the hydrolysis of organometallic compounds. The final structure of the nanoparticles is usually not obtained until after or during a subsequent calcination following the precipitation.
The targeted control of the crystallization process can be influenced by the composition of the educt(s). An important factor here—in particular when used in the catalysis of such nanoparticles—is the crystallite size (R. Schlögel et al., Angewandte Chemie 116, 1628-1637, 2004). However, it has hitherto been almost impossible, by means of wet-chemical production methods, in particular by means of the so-called basic hydroxide precipitation, to accordingly optimize the precipitation method in respect of the desired nanoparticles and their properties, in particular their average particle-size distribution.
Mechanical production methods for the synthesis of nanoparticles have therefore also been considered. This is carried out for example by intensive grinding of inhomogeneous particles to homogeneous particles, which however often also leads to undesired phase transformations to the point where particles become amorphous due to the pressure exerted on the particles.
However, the particles formed in the process are not present in a uniform homogeneous size distribution, because the very small particles formed display a marked tendency to reagglomerate.
Further access to nanoparticles is via thermophysical methods as disclosed for example in WO 2004/005184. These are typically based on the introduction of thermal energy into solid, liquid or gaseous starting compounds. Here, the so-called plasmapyrolytic spraying process (PSP) of the abovenamed WO 2004/005184 in which the starting substances are sprayed in an oxyhydrogen flame and decomposed is particularly widely used. A typical application for the PSP process is in the production of nanocrystalline silicon dioxide in which readily volatile organosilicon compounds are sprayed in an oxyhydrogen flame.
Furthermore, in the synthesis of nanoparticles the so-called plasma synthesis method is often used in which the starting substances are evaporated in a plasma up to 6,000 K in temperature. Further methods known from the state of the art are for example CVD methods in which gaseous educts are reacted, wherein typically non-oxidic powders and mixed oxidic compounds with different phase structures also form.
Nanoparticulate compositions are also widely used for example in the production of electrode materials for secondary batteries as described for example in EP 1 553 647 A1. In this patent application, in particular the production of lithium iron phosphate is described, wherein the material forms mostly aggregates>1 μm in size. Particles that are as finely dispersed as possible are also be desirable in particular for use as cathode material.
Similar problems result in the production, disclosed in US 2002/0192137, of nanoscale and submicron particles in a flow reactor by means of laser irradiation, wherein complex oxides such as for example lithium phosphorus oxide nitride, lithium iron manganese phosphate, calcium phosphate, aluminium phosphate etc. also form. According to US 2002/0192137, these nanoparticles are likewise used as material for battery applications. A production of in particular lithium iron phosphates by the aqueous route in order to obtain nanoparticles is disclosed in WO 2006/116251, but in the case of lithium iron phosphate a precipitation by means of hydroxide is advised against and the so-called carbonate precipitation is recommended for the starting materials.
The production of lithium iron phosphate (LiFePO4) is known in particular from U.S. Pat. No. 5,910,382 by Goodenough et al. This material is currently the most promising material for use in secondary lithium ion batteries. Furthermore, WO 02/27823 and WO 02/27824 describe the production of LiFePO4 starting from iron phosphate by reaction with lithium carbonate in the presence of a carbon monoxide atmosphere.
DESCRIPTION OF THE INVENTION
An object of the present invention was therefore to provide extremely finely dispersed nanoparticulate compositions which do not form agglomerates or larger agglutinations. The term “nanoparticulate” usually describes particles with an average particle size of ≦500 nm, while a size range of from 1-100 nm is mostly given for nanoparticles (cf. e.g. Paschen, H., Coenen, C., Fleischer, T., Grünwald, R., Oertel, D., Revermann, C.; Nanotechnologie—Forschung, Entwicklung, Anwendung; Springer-Verlag; Berlin, Heidelberg, New York 2004).
This problem is solved according to aspects of the invention by a nanoparticulate composition which comprises non-aggregated nanoparticles, isolated from one another, of a transition metal compound with a particle-size distribution of d90≦10 μm, quite particularly preferably d90≦5 μm. According to aspects of the invention, the transition metal compound is both a pure (“binary”) transition metal compound, i.e. composed of a single anion or cation, and a mixed (“polynary”) or “doped” transition metal compound which can have several transition metal cations and/or anions.
The term “non-aggregated” means according to aspects of the invention that no particles which consist of several individual particles, i.e. which form so-called agglomerates (“secondary particles”) and have a particle size of more than 15 μm, are present in the nanoparticulate composition. In other words, the composition according to aspects of the invention therefore consists only of so-called primary particles.
The particle-size distribution of the composition according to aspects of the invention is preferably monomodal and quite particularly preferably the d50 value of the nanoparticles according to aspects of the invention is 0.2 to 1 μm. It was surprisingly found that the nanoparticulate composition comprises almost exclusively finely-crystalline nanoparticles and no amorphous particles are present.
The nanoparticulate composition preferably comprises a material which is selected from oxides, phosphates and sulphates of chromium, titanium, iron, nickel, molybdenum, tungsten, zirconium, hafnium, tantalum, niobium, cerium and vanadium or mixtures thereof. Iron phosphates such as FePO4.2H2O (iron(III)phosphate) or Fe3(PO4)2 (iron(II)phosphate), titanium dioxide (TiO2), Li4Ti5O12 and LiFePO4 and their doped compounds may be named as particularly preferred non-limiting specific examples.
Iron(III)phosphate is already long-known. For example, a production method is described in GB 962 182. However, the iron(III)phosphate of the state of the art (FePO4.2H2O) has at best an average particle size d50 of from approx. 10 to 20 μm. To date, smaller particle sizes have been unobtainable or obtainable only with difficulty due to the production methods and the high levels of contamination with sulphates.
The size distribution of the nanoparticles according to aspects of the invention in particular from the abovenamed materials is monomodal in quite particularly preferred specific embodiments. In particular the FePO4 and Fe3(PO4)2 particles have a quite particularly preferred average particle-size distribution d50 of from 0.3 to 0.8 μm, more preferably 0.4 to 0.7 μm, which is well below the particle-size distributions d50 of all previously known iron(III) and iron(II)phosphates of the state of the art.
Unlike the sulphate-containing iron(III)phosphates mostly used to date, which is almost inevitable due to the use of iron sulphate as starting material, the particulate composition according to aspects of the invention comprising FePO4.2H2O is almost sulphate-free. “Almost” means here that, using currently customary analysis methods, no sulphate can be detected within the limits of measurement accuracy.
A further important aspect of the present composition according to aspects of the invention comprising FePO4.2H2O or Fe3(PO4)2, TiO2 or LiFeO4 is that, as stated above, the particles of this composition are finely crystalline and are not present in an amorphous state or have no amorphous particles whatever, as typically occurs in most other nanoparticulate FePO4 or Fe3(PO4)2 and TiO2 or LiFePO4 compounds of the state of the art.
In an advantageous development of the present invention, the composition according to aspects of the invention also comprises a surface-active agent.
Surprisingly, it was found that the presence of the surface-active agent leads to the individual nanoparticles in the composition remaining separated from one another, i.e. isolated after the final drying, whereby the composition according to aspects of the invention can therefore be used as particularly finely particulate powder which does not aggregate and agglomerate, not even under typical agglomeration conditions such as increased ambient moisture etc. This affects in particular nanoparticles based on metal or transition-metal phosphates, oxides, carbonates and sulphates.
The surface-active agent is preferably ionic in character, wherein, depending on the chemical structure and property of the nanoparticles, the ionic character of the surface-active agent can vary from cationic to anionic.
It was furthermore found that the surface-active agent can be present in a quantity of 0.01 to 2 wt.-% relative to the overall mass of the composition. Below 0.01 wt.-% it is no longer guaranteed that the nanoparticles remain separated from one another and do not aggregate or agglomerate. Above 2 wt.-% agglomerates likewise form as a result of the increasing quantity of surface-active agents. However, preferably no more than 1 wt.-% should be present, as otherwise filtration is made difficult.
The surface-active agent, in particular in the case of compositions according to aspects of the invention comprising TiO2, Fe3(PO4)2, LiFePO4 and FePO4, preferably has a weakly cationic character, as have for example the surface-active agents of the Praestol flocculant series from Stockhausen GmbH & Co.
It proved advantageous that the surface-active agent with weakly cationic character is comprised in a quantity of 0.01 to 1 wt.-% relative to the weight of the overall composition, wherein finely-dispersed crystallites of the corresponding material, in particular TiO2, LiFePO4, Fe3(PO4)2 and FePO4.2H2O are then present. Above 1 wt.-% of the surface-active agent, a simple filtration of the product in the method according to aspects of the invention described below is no longer possible and almost exclusively agglutinated agglomerates are obtained.
In the production of TiO2 by hydrolysis of Ti(IV) compounds, it was also already known to add cationic polyelectrolytes (EP 260 664 A2), however quantities of more than 4, even more preferably of more than 5.5 wt.-% relative to the weight of the overall composition were required. The small quantities of surface-active agents used according to aspects of the invention are unprecedented.
Furthermore, an object of the invention is achieved by a method for the production of a nanoparticulate composition as defined above, wherein the nanoparticles are precipitated in solution and a surface-active agent is added after the precipitation of the nanoparticles.
This method for the production of a nanoparticulate composition comprising an oxide, carbonate, sulphate or phosphate of a transition metal includes the steps of
a) providing an acid aqueous solution of a transition metal starting compound;
b1) optionally, adding an alkali hydroxide solution;
b2) adding an acid with a suitable anion;
c) adding a surface-active agent after the start of the precipitation of the precipitate;
d) filtering the precipitated nanoparticulate composition.
By “alkali hydroxide” is meant according to aspects of the invention KOH or NaOH solutions.
The term “suitable anion” means that the anion forms a precipitate insoluble in the solvent used with the transition metal starting compound.
For example, in the production of nanoparticulate TiO2 only a hydrolysis with water is required which thus in other words functions as “acid”.
Step b1) is optional because, as e.g. in the case of TiO2 addition of a base is not necessary because TiO2 already forms through hydrolysis.
The nanoparticles obtained by means of the method according to aspects of the invention precipitate as binary or polynary compounds, with the result that an almost unlimited number of compounds can be produced by means of the method according to aspects of the invention.
At least one, preferably the first step a) (the other steps then take place at room temperature), more preferably all steps a) to c) of the method steps are carried out at a temperature in the range of from 60-170° C., preferably 60-150° C., most preferably 60-110° C.
The addition of the surface-active agent in step c) is typically carried out after the start of the precipitation of the precipitate, quite preferably after the end of the precipitation and leads to a clearly recognizable flocculation of the precipitate which before the addition had the form of an extremely finely dispersed suspension. As a result of the flocculation, an easy filtration is possible according to aspects of the invention via filter media customary in the trade without e.g. centrifuges etc. having to be used.
Following the filtration, the nanoparticulate composition can still be dried at temperatures of ≦250° C.
The starting compounds of the binary or polynary nanoparticles are preferably used in water-soluble form in order to guarantee an exact stoichiometry and ease of handling.
It was surprisingly found that, as a result of the method according to aspects of the invention, in particular the addition of a surface-active agent after the start of the precipitation, finely-crystalline, isolated, non-agglomerated nanoparticles with particle diameters of 0.3 to 0.8 μm, quite particularly 0.4 to 0.7 μm, are obtained, which was not to be expected on the basis of the hydroxide precipitation route used here. This is true in particular for example for FePO4.2H2O, Fe3(PO4)2, LiFePO4 and TiO2. The term “after the start of the precipitation” also includes according to aspects of the invention the time that the addition, as already explained above, takes place after the end of the precipitation process.
It was known e.g. in the case of FePO4.2H2O (P. Reale and B. Scrosati Chem. Mater. 5051 2003) that iron phosphate can be obtained starting from FeCl3 with H3PO4 at a starting concentration of 0.009 mol/l FeCl3.H2O and 0.0027 mol/l H3PO4, wherein three structurally different phases with the chemical formula FePO4.2H2O form, namely strengite, metastrengite I and metastrengite II, which precipitate at different pHs.
According to this citation, strengite forms when 0.04 molar NaOH (pH=3-4) is added, metastrengite I without further addition (pH=1-2) and metastrengite II when 0.5 molar HCl (pH=0-1) is added. The reaction times to reach the pure phases increase from strengite at two days via metastrengite I at 7 days to metastrengite II at 12 days. The authors furthermore also describe mixed phases under strongly acid conditions (pH=0-1) and a shorter reaction time than 12 days. The strengite phase also occurs as a natural mineral with the same name, metastrengite II can be equated with the naturally occurring mineral phosphosiderite. Metastrengite I is described neither as natural nor as synthetic phase.
Problems result in particular because of the poor filterability of the product and as a result of the different phases described in the state of the art.
Unlike the abovementioned results of Reale and Scrosati, it was surprisingly not observed with the method according to aspects of the invention that strengite FePO4 forms first and metastrengite I and metastrengite II phases after a longer reaction time.
With the method according to aspects of the invention, the metastrengite I phase typically forms immediately.
In a preferred embodiment in which the FeCl3 solution, preferably also the NaOH or KOH solution, is heated to a temperature of from 60 to 170° C., more preferably 60 to 150° C., most preferably 60-110° C. and the FeCl3 solution has a concentration of 30 to 50%, the method according to aspects of the invention, in the case of the production of FePO4.2H2O starting from iron(III)chloride, NaOH or KOH and phosphoric acid, displays a high yield of more than 90%, wherein an extremely finely-dispersed crystalline material of primary particles without agglomerates (secondary particles) or aggregates forms.
The disadvantage when using iron(III)chloride is that the educt has a high chloride content, as chlorides have a strong corrosive effect both in production and in later uses. During production, typically no customary metal containers can be used, with the result that for example at least the inside must be given an acid-resistant coating. Furthermore, it was previously believed that the obtained material must be washed vigorously in order to obtain a low chloride concentration of the product.
In the state of the art, the use of caustic soda solution or caustic potash solution as precipitant was previously advised against in the synthesis of transition metal compounds, as non-filterable products form and the obtained raw product is strongly agglomerated above certain concentrations of caustic soda or caustic potash solution.
According to aspects of the invention, the nanocrystalline iron(III)phosphate with the particle-size distribution according to aspects of the invention is obtained in particular when, through addition of the caustic soda or caustic potash solution to the iron(III)chloride solution, iron(III)hydroxide is precipitated as an intermediate product in the heat in the reaction solution, and then reacts further with phosphoric acid to iron(III)phosphate. Without intermediate precipitation of iron(III)hydroxide, too few condensation nuclei form, which results in the formation of larger particles.
NaOH or KOH solution is preferably used in a concentration of approx. 2 mol per mol Fe, which leads to better results in the intermediate precipitation of iron hydroxide.
The FePO4.2H2O or Fe3(PO4)2 obtained by means of the method according to aspects of the invention is particularly well suited to use in the production of lithium iron phosphate or mixed (doped) lithium iron transition metal phosphates e.g. in solid-state methods known from the state of the art and also in so-called hydrothermal methods likewise largely known from the state of the art.
Furthermore, an object of the present invention is achieved with a method for the production of nanoparticulate LiFePO4 comprising the reaction of

    
    
        a) a nanoparticulate composition according to aspects of the invention comprising FePO4.2H2O with
        b) a stoichiometric quantity of a lithium compound selected from LiOH, Li2O, lithium acetate, lithium oxalate or Li2CO3 

under pyrolytic conditions, i.e. in a solid-state reaction, wherein in preferred developments additionally a transition metal compound is added, wherein the transition metal M is selected from Co, Ti, Ni, V, W, Pd, Ru, Cu, Mn, Ba, Sr, Nd, Mg. Typical compounds are their phosphates, carbonates, oxalates, nitrates, acetates, hydroxides, carboxylates or oxides. Thus the corresponding doped lithium iron phosphates LiFe1-xMxPO4 with x<1 can be obtained, wherein M can also be a mixture of several of the abovenamed transition metals, as described e.g. in EP 1,325,525 A1, EP 904 607 B1, US2003/0082454, reference to the full disclosure content of which is made here.

    
    


According to aspects of the invention, the method for the production of undoped and doped lithium ion phosphate can also be carried out hydrothermally, i.e. in solution, typically in aqueous solution, in which

    
    
        a) a nanoparticulate composition according to aspects of the invention comprising Fe3(PO4)2. is hydrothermally reacted with
        b) a stoichiometric quantity of a lithium compound selected from LiOH, Li2O, lithium acetate, lithium oxalate or Li2CO3 as well as a phosphate source.
    
    


By adding a water-soluble transition metal compound, wherein the transition metal M is selected from Co, Ti, Ni, V, W, Pd, Ru, Cu, Mn, Ba, Sr, Nd, Mg, the corresponding doped lithium iron phosphates LiFe1-xMxPO4 with x<1 can also be obtained on this synthesis route, wherein M can also be a mixture of several of the abovenamed transition metals. Typical soluble compounds include, but are not limited to, the nitrates, acetates, chlorides, carboxylates, bromides, sulphates, hydroxides, phosphates of the abovenamed transition metals (see e.g. WO 2005/051840 A1). For example, phosphoric acid (in particular for the production of undoped LiFePO4) or also the corresponding phosphates of the mixed doping metal(s) serve as phosphate source according to aspects of the invention.
It is advantageous if the method steps a) to c) in the hydrothermal method are carried out at a temperature of from 60° C. to 170° C., particular preferably of from 100° C. to 150° C., as the total yield of the precipitation or reaction increases compared with when operating at room temperature.
Likewise, according to aspects of the invention, Li4Ti5O12 can be produced both pyrolytically and also hydrothermally, wherein a lithium compound, selected from LiOH, Li2O, lithium acetate, lithium oxalate or Li2CO3 is reacted in a stoichiometric quantity with a nanoparticulate composition according to aspects of the invention comprising TiO2 at a temperature in the range of from 500-750° C. in a hydrothermal process.
It was surprisingly found that the nanoparticulate properties of the composition obtained according to aspects of the invention comprising e.g. FePO4.2H2O, Fe3(PO)2 and TiO2 are retained even after calcination of the composition according to aspects of the invention in the LiFePO4 or Li4Ti5O12 produced by means of these calcined products in the method according to aspects of the invention as well as in their doped derivatives, with the result that in the case of the starting compound the addition of a surface-active agent already has a positive effect on the agglomeration behaviour even during the subsequent synthesis of e.g. LiFePO4 or Li4Ti5O12 or their doped derivatives. In other words extremely finely-dispersed nanoparticulate, crystalline pure or doped LiFePO4 or Li4Ti5O12 is obtained starting from FePO4, Fe3(PO4)2 or TiO2 precipitated with a surface-active agent according to aspects of the invention.
According to aspects of the invention, extremely finely-dispersed materials can thus be obtained which retain their fine dispersion even after further reaction or transfer this to the product obtained by further reaction.
In preferred embodiments, the synthesis is carried out in the presence of an additional carbon source, as described e.g. in EP 1 049 182 A1, reference to the full disclosure content of which is made here.
In quite particularly preferred embodiments, the surface-active agent which is already comprised in a preferred composition according to aspects of the invention (which has not been calcined) is used as carbon source, with the result that the addition of a further carbon source can advantageously be dispensed with. Further access to carbon-coated nanoparticles, for example LiFePO4, Li4Ti5O12 or their doped derivatives, is thereby provided.



BRIEF DESCRIPTION OF THE FIGURES
The invention is described in more detail below with reference to drawings and embodiment examples which are not, however, to be considered limiting.
There are shown in:
FIG. 1 an SEM photo of LiFePO4 which was obtained with the composition according to aspects of the invention comprising iron phosphate;
FIG. 2 an SEM photo of LiFePO4 which was obtained according to the state of the art from FePO4 without the addition of a surface-active agent;
FIG. 3 an SEM photo of LiFePO4 which was obtained starting from FePO4.2H2O;
FIG. 4 in a diagram the loadability and capacity of LiFePO4 obtainable from various starting materials;
FIG. 5 in a diagram the voltage characteristic when charging and discharging the first 35 cycles of LiFePO4 with FePO4.2H2O obtained according to aspects of the invention as precursor;
FIG. 6 an SEM photo of a composition according to aspects of the invention which comprises nanoparticulate FePO4.2H2O;
FIG. 7 an SEM photo of FePO4.2H2O without the addition of a surface-active agent.



DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIG. 1 shows an SEM photo of LiFePO4 (sample number ALEP 46—3) which was produced from nanoparticulate FePO4 obtained according to aspects of the invention analogously to the method described in CA 2320661 according to Example 2 below and displays clearly finely-crystalline discrete particles as well as the starting substance FePO4.2H2O. The fine crystallinity of FePO4 was thus “transferred” to LiFePO4.
FIG. 2 shows LiFePO4 (sample ALEP 46—1) which was obtained starting from FePO4.2H2O as in FIG. 1, in which no surface-active agent was added during the production, and clearly shows an agglomeration of the particles (unlike the finely-crystalline, discrete particles in FIG. 1) to larger aggregates.
FIG. 3 shows an LiFePO4 produced according to the same method from commercially available FePO4.2H2O (Budenheim), which, compared with FIG. 1 and FIG. 2, displays in particular much larger, coarser individual particles.
FIG. 4 shows the loadability and capacity of LiFePO4 produced according to Example 2, which was obtained starting from various FePO4.2H2O starting materials.
There it is can be seen that the particle size of the particles has a marked effect on the loadability and capacity of the samples.
The LiFePO4 sample (Alep 46—3) produced from FePO4.2H2O produced according to aspects of the invention has a higher capacity than the sample from FIG. 3 (JM0700) which was obtained from commercially available FePO4.2H2O from Budenheim.
LiFePO4 produced hydrothermally according to WO 2005/051840 A1 (available from Sud-Chemie AG) (PD21) is comparable. The sample Alep 46—3 displays a somewhat poorer capacity PD 21 only from 8C.
It can also be seen in FIG. 5 that LiFePO4, which was produced by means of FePO4.2H2O obtained by the method according to aspects of the invention according to Example 2, has a good cycle stability with a flat plateau at approximately 3.5 volts. After 35 cycles, there is a decrease in capacity of approx. 4 to 3%. The starting capacity of the obtained LiFePO4 sample was 98% of the theoretical.
FIG. 7 shows an SEM photo of FePO4.2H2O which was likewise obtained by means of hydroxide precipitation, but without the addition of a surface-active agent. Wholly unlike the FePO4.2H2O composition produced according to aspects of the invention according to FIG. 6, a marked agglomeration is to be observed, against which the composition according to aspects of the invention (0.05% surface-active agent) in FIG. 6 clearly displays finely-crystalline particles without agglomeration.
Example 1
Synthesis of FePO4.2H2O
The method according to aspects of the invention for the production of a nanoparticulate composition according to aspects of the invention is explained in more detail with reference to a synthesis of FePO4.2H2O.
The method was carried out in a hydrothermal reactor (Thale reactor, 200 l). The synthesis typically took place as follows:
146 kg 40% FeCl3 solution (58.9 kg FeCl3, i.e. 360 mol) was introduced into the reactor and a further 125 l water added. The mixture is then heated to a temperature of approx. 70° C.
56.2 kg 50% NaOH solution (28.1 kg NaOH, 702 mol) was then added accompanied by stirring, whereupon the temperature increased to approx. 95° C.
43.2 kg 80% H3PO4 (34.6 kg H3PO4, i.e. 353 mol) was then added immediately. The temperature remained at approx. 95° C. H3PO4 was used in a hypostoichiometric quantity of approx. 2% relative to FeCl3.
The mixture was then heated to approx. 100° C. and stirred for 21⁄2 hours. The temperature was kept at this value.
In this reaction, the iron concentration in the system was approximately 0.9 mol/l and the neutralization content was approximately 65% (1.95 mol NaOH per mol Fe).
After the stirring was ended, the solution and the formed yellow suspension were cooled to approx. 30° C., whereupon iron phosphate was obtained as a yellow suspension in a strongly acid solution.
A 0.2% aqueous solution of the weakly cationic surface-active agent Praestol 611 BC (Stockhausen GmbH & Co., Germany) was then added as follows to the cooled suspension:
The solution of the surface-active agent (0.05% surface-active agent relative to the dry mass of the iron phosphate dihydrate) was added slowly to the FePO4.2H2O suspension over a few minutes. The slightly viscous suspension was then filtered off and washed with ionized water until the conductivity of the washing water was less than 400 μS/cm.
The d50 value was 0.4 μm. The material was finely crystalline without showing agglomerates (FIG. 6).
Example 2
Synthesis of LiFePO4 (Pyrolytic Reaction)
LiFePO4 was produced by reaction of the FePO4.2H2O and Li2CO3 obtained in Example 1 (available under the name Lithiumcarbonat Special PC/US 250 ACU from Pharma & Chemie GmbH) in the presence of hydrogen. In a first step, stoichiometric quantities of the two starting compounds were ground in isopropanol and then heated stepwise in an oven (6° C./minute to a temperature of 700° C.) under an atmosphere of 8% hydrogen in argon. This temperature was maintained for an hour. The obtained product was then cooled to room temperature within 40 minutes.
Throughout the thermal treatment and likewise during the reduction of the temperature, the gas flow of the reduction gas was retained. The total duration of the thermal treatment was approximately three and a half hours.
The structure of the obtained LiFePO4 was determined by means of powder diffractometry and the obtained peaks of the spectrum corresponded to that of pure triphylite LiFePO4.
The d50 value was 0.5 μm. The material was finely crystalline without showing agglomerates (FIG. 1).
Example 3
Synthesis of LiFePO4 with Carbon Coating
The LiFePO4 obtained in Example 2 was impregnated with a solution of cellulose acetate (39.7 percent by weight acetyl content with an average molecular weight MW of 50,000) in acetone. The quantity of cellulose acetate was approx. 5 percent by weight relative to the LiFePO4 to be treated. The acetone was drawn off and the obtained solid heated to 700° C. in a heating furnace under an argon atmosphere with a heating rate of 6° C./minute. This temperature is then maintained for an hour and the obtained product then gradually cooled to room temperature under a protective gas. The obtained sample contained 1 percent by weight carbon.
The electric conductivity of the obtained product was greater than 1×10−8 S/cm.
The d50 value was 0.6 μm. The material was finely crystalline without showing agglomerates.
Example 4
Synthesis of LiFePO4 with Carbon Coating
LiFePO4 coated with carbon was obtained from the FePO4.2H2O, Li2CO3 obtained in Example 1 (available under the name Lithiumcarbonat Special PC/US 250 ACU from Pharma & Chemie GmbH) and a carbon source. The carbon source was cellulose acetate as in Example 3 (39.7 percent by weight acetyl content, average molecular weight MW 50,000), wherein cellulose acetate was used in a quantity of 5 percent by weight relative to the quantity of FePO4.2H2O. Overall, the quantity of cellulose acetate was 4.2% relative to the weight of the mixture of FePO4.2H2O and Li2CO3. The mixture was stirred in isopropanol, the solvent removed and the mixture subjected to the thermal treatment specified in Examples 2 and 3.
The reductive atmosphere was composed of 8% hydrogen in argon.
The structure of the obtained product was determined by means of powder diffractometry and the reflexes correspond to those of pure LiFePO4.
The produced sample is composed of very fine particles isolated from one another of the order of magnitude of 1 μm which are covered with a thin layer of carbon.
The electric conductivity of the obtained product was greater than 1×10−8 S/cm.
The d50 value was 0.6 μm. The material was finely crystalline without showing agglomerates.
Example 5
Synthesis of Carbon-Coated LiFePO4 
The FePO4.2H2O obtained from Example 1 was mixed in stoichiometric quantities with Li2CO3 (available under the name Lithiumcarbonat Special PC/US 250 ACU from Pharma & Chemie GmbH) as well as 5 percent by weight relative to the whole mixture of FePO4 (2H2O, Li2CO3 and a polymeric carbon source polyethylene-block-poly(ethylene glycol) (50% polyethylene) (Aldrich). This mixture was stirred in isopropanol and then put in the oven after drying and subjected to the thermal treatment described in Examples 2 and 3.
The electric conductivity of the obtained product was greater than 1×10−8 S/cm.
The d50 value was 0.5 μm. The material was finely crystalline without showing agglomerates.
Example 6
Electrochemical Measurements
Electrochemical measurements were carried out on the LiFePO4 compound obtained according to aspects of the invention from Example 5.
The measurement of the capacity in the first cycle showed values of 95 to 97.5% of the theoretical capacity.
The LiFePO4 obtained according to aspects of the invention has a very good cycle stability with a flat plateau at −3.5 V (FIG. 5).
After 35 cycles a fall of only approx. 2% in capacity could be measured.
Example 7
Synthesis of TiO2 
13.2 ml H2SO4 (96%) and 11.2 ml TiCl4 (98%) were added dropwise accompanied by stirring to 100.2 ml HCl (37%), in order to obtain a solution.
500 ml distilled H2O was then added, further distilled water added, until a clear and colourless solution was obtained.
The strongly acid solution of TiCl4 was then heated to approx. 108° C.
After approx. ten minutes at 100° C., a slightly opalescent precipitate formed, becoming a milky suspension. When the first precipitate settled out a 0.2% Praestol 611 BC solution (Stockhausen GmbH & Co, Germany) was added and the solution kept at this temperature for a further two hours.
The precipitate was then filtered off, washed with distilled water and dried at 120° C.
After the drying step, a calcining step was also carried out at 1200° C.
The yield was approx. 6.54 g TiO2 in anatase form.
The d50 value was 0.5 μm. The material was finely crystalline without showing agglomerates.
Example 8
Production of Li4Ti5O12.
147.8 g Li2CO3 (2 mol) and 399.4 g TiO2 from Example 7 were mixed. A Li2CO3 excess of approx. 2 to 5% was used. The lithium carbonate is commercially available under the name Lithiumcarbonat Special PC/US 250 ACU from Pharma & Chemie GmbH.
Distilled water was then added accompanied by stirring until a homogeneous viscous mixture was obtained.
The thus-obtained mixture was dried at room temperature and the thus-obtained dried mixture then ground very fine in a grinding treatment, for example with a Fritsch disk mill with a gap width of typically 0.25 mm.
The mixture was then calcined for four hours at approx. 950° C. in a Navatherm-Ceramotherm N45040 oven.
The obtained product was then characterized by powder diffraction analysis and the reflexes correspond to that of pure lithium titanate Li4Ti5O12. No detectable quantities of rutile were found in the end-product.
The d50 value was 0.7 μm. The material was finely crystalline without showing agglomerates.
Example 9
Synthesis of Carbon-Coated Li4Ti5O12 
The lithium titanate obtained in Example 8 was ground once more with an air-jet (AFG 100 air-jet mill), and stirred with a cold concentrated lactose solution to a viscous suspension. The suspension was dried at 100° C. for 12 hours and optionally ground in a Fritsch disk mill with a gap of 0.25 mm.
The ground material was heated to 750° C. under protective gas in a so-called Linn furnace and then calcined for three hours at 750° C.
The obtained product was given a final grinding in a Fritsch mill with a 0.8 mm screen.
The obtained product corresponded to the carbon-coated particles described in WO02/46101, except that the particles obtained according to aspects of the invention have a particularly fine particle distribution of 0.3 to 0.8 μm and also displayed no agglomeration behaviour.
It is also to be observed in this example that, through the addition of the flocculant, the finely crystalline character of the originally obtained TiO2 was also retained in the end product Li4Ti5O12 both with and without carbon coating. It goes without saying that the further carbon sources described in WO02/46101 can also be used instead of lactose.
The d50 value was 0.7 μm. The material was finely crystalline without showing agglomerates.
Example 10
Synthesis of LiFePO4 (Hydrothermal Reaction)
1. Production of the Precursor Suspension
8.746 kg LiOH.H2O was dissolved in approx. 50 l deionized water in a container and the solution introduced first into a 200-l autoclave with stirrer via a monopump and stirred at 40 to 80 rpm.
18.61 kg FeSO4.7H2O was then dissolved in 30 to 35 l deionized water in a vessel and 7.8 kg 85% phosphoric acid slowly added accompanied by stirring. The acid solution was pumped into the autoclave via the monopump. A mixture of Fe3(PO4)2.8H2O and Li3PO4 immediately began to precipitate in the autoclave.
The suspension formed was then cooled to approx. 30° C. and a 0.2% aqueous solution of the weakly cationic surface-active agent Praestol 611 BC (Stockhausen GmbH & Co., Germany) added to the suspension. The addition took place dropwise over a few minutes, preferably approx. 5 to 10 minutes.
Unlike the synthesis without addition of the surface-active agent, a finely-crystalline suspension forms instead of the previously observed pudding-like consistency of the suspension, as was described e.g. in WO 2005/051840 A1.
The dispersion or grinding treatment required in the international patent application described here as well as the pumping round of the highly-viscous solid paste are dispensed with in the present method according to aspects of the invention.
After the precipitation had taken place the Fe3(PO4)2.8H2O/Li3PO4 suspension was pumped round for a further approx. 2 hours. An ideal mixture of the precipitated precursor substances Fe3(PO4)2.8H2O and Li3PO4 is thus achieved.
Typically a so-called centrifugal pump can be used.
After the thorough mixing of the two precursor substances by means of pumping round, the autoclave was sealed in pressure-tight manner and heated to 160° C. for 2 hours accompanied by constant stirring at 90 to 100 rpm and kept at this temperature for 10 hours. The reaction mixture was then cooled to room temperature within 3 to 4 hours and the obtained finely-crystalline LiFePO4 suspension filtered off and washed with ionized water until the conductivity of the washing water was less than 4 μS/cm.
The d50 value was 0.5 μm. The material was finely crystalline without showing agglomerates.
Example 11
Synthesis of Carbon-Coated LiFePO4 
The LiFePO4 obtained in Example 10 was coated with carbon as in Example 3. Instead of cellulose acetate, a corresponding quantity of lactose monohydrate was used as carbon source.
Typically approx. 90 g lactose monohydrate in 350 g deionized water was used to achieve an approx. 2% carbon coating on the finished finely-crystalline product per kilogram of dry LiFePO4 powder.
The electric conductivity of the obtained product was greater than 1×10−8 cm. The thus-obtained sample contained approx. 2.2 percent by weight carbon.
The d50 value was 0.6 μm. The material was finely crystalline without showing agglomerates.

## Claims

1. A nanoparticulate composition in the form of a dried, finely particulate powder, comprising non-agglomerated nanoparticles of a transition metal compound with a particle-size distribution d90≦10 μm and d50 of 0.4 to 0.7 μm, wherein the nanoparticles are composed of a material comprising FePO4.2H2O, Fe2(PO4)2, or mixtures thereof; and wherein the composition further comprises a surface-active agent in a quantity of 0.01 to 1 wt. % relative to the total weight of the composition.

2. Composition according to claim 1, wherein the nanoparticles are present in crystalline state.

3. Composition according to claim 1, wherein the nanoparticles have a carbon-containing coating.

4. Composition according to claim 1, wherein the composition is sulphate-free.

5. Composition according to claim 1, wherein the surface-active agent has an ionic character.