Patent Application
20190173084
Embodiments of the invention generally relate to a cathode active material for a high voltage secondary battery, a secondary battery where the cathode is fully or mainly operated above 4.4 V vs. Li/Li+ comprising the cathode active material and a method for preparing a cathode active material.
Lithium-ion batteries are common in consumer electronics. They are one of the most popular types of rechargeable batteries for portable electronics, with a high energy density, small memory effect, and only a slow loss of charge when not in use. For the same reason they are also considered one of the best technologies for use in electrical vehicles and for storage of electrical energy from intermittent sources of renewable electrical energy. Lithium ion battery materials are under continued development in order to further refine the batteries. Improvements typically relate to one or more of the following: increasing the energy density, cycle durability, lifetime and safety of the batteries, shortening the charging time and lowering the cost of the batteries.
Oxide materials containing lithium and transition metals that can be charged to high voltage (cathode charged to >4.4 V vs. Li/Li+) are suitable as cathode active materials. Due to the high potential, batteries made from such a material has a higher energy density compared to batteries made with other battery materials, such as lithium cobalt oxide and lithium iron phosphate. Batteries based on high voltage materials can be used in high energy and high rate applications.
Another important factor for the choice of materials for the Lithium ion battery (LiB) is the abundance of their components in the earth crust securing long term availability and cost reduction, due to which materials based on iron and manganese are of great interest. Especially manganese oxides constitute a promising group of cathode active materials, because manganese is a low priced and non-toxic element. In addition, manganese oxides have a rather high electric conductivity together with a suitable electrode potential. Among the lithium manganese oxides, the layered LiMnO2 and the spinel-type LiMn2O4 (LMO) are the most prominent ternary phases. An advantage of the latter one in comparison to the layered phase is a higher potential of about 4.0 V against Li/Li+, whereas LiMnO2 delivers only 3.0 V in average. The LiMn2O4 lattice offers three-dimensional lithium diffusion, resulting in a faster uptake and release of this ion. The diffusion of Li+ in doped LMO spinels is also equally fast in all three dimensions.
Among the transition metal doped LiMn2O4 spinel materials, LiNi0.5Mn1.5O4(LMNO) is a very promising material: It operates mainly at a relatively high voltage of 4.7 V vs. Li/Li+ due to the electrochemical activity of the Ni2+/Ni4+ redox couple. LiNi0.5Mn1.5O4 has a theoretical specific discharge capacity of 147 mAh/g and therefore an attractive theoretical energy density of 4.7 V*147 Ah/kg=691 Wh/kg active material, referring to lithium metal. By replacing 25% of the manganese ions with nickel, there is in theory no Mn3+ left in the structure. The spinel crystal structure of LNMO cathode active material is a cubic close-packed crystal lattice with space groups of P4332 for the ordered phase and Fd-3m for the disordered phase. The spinel material may be a single disordered or ordered phase, or a mix of both (Adv. Mater. 24 (2012), pp 2109-2116).
LNMO materials are lithium positive electrode active materials dominated by the Ni doped LiMn2O4 spinel phase, which more specifically may be characterized by the general formula LixNiyMn2−yO4 with typical x and y of 0.9≤x≤1.1 and 0≤y≤0.5, respectively. The formula represents the composition of the cathode active spinel phase of the material. Such materials may be used for e.g. portable electric equipment (U.S. Pat. No. 8,404,381 B2), electric vehicles, energy storage systems, auxiliary power units (APU) and uninterruptible power supplies (UPS).
Electrode active LNMO materials for lithium ion batteries are described abundantly in the literature. Thus, U.S. Pat. No. 5,631,104 describes insertion compounds having the formula Lix+1MzMn2−y−zO4 wherein the crystal structure is spinel-like, that can reversibly insert significant amounts of Li at potentials greater than 4.5 V vs. Li/Li+. M is a transition metal in particular Ni and Cr, 0≤x≤1, 0≤y<0.33, and 0<z<1.
U.S. Pat. No. 8,956,759 (Y. K Sun et al.) describes a 3V class spinel oxide with improved high-rate characteristics which has the composition Li1+xMyMn2−yO4−zSz (0≤x≤0.1; 0.01≤y≤0.5, 0.01≤z≤0.5) and M is Mn, Ni or Mg, wherein the spinel oxide is composed of spherical secondary particles having a particle diameter of 5-20 μm obtained from aggregation of primary particles having a particle diameter of 10-50 nm. Further disclosed is a method for preparing the 3V class spinel oxide by carbonate co-precipitation of starting materials, addition of elemental sulfur, followed by calcination. The 3V class spinel oxide is spherical and has a uniform size distribution.
The oxide of U.S. Pat. No. 8,956,759 described above has the disadvantage, well-known to those skilled in the art that the relative high surface area arising from the very small size of primary particles leads to relative fast electrolyte decomposition on the surface of the spinel oxide at high voltages as well relatively fast dissolution of metals from the cathode in the electrolyte, and thereby to degradation of a battery comprising the spinel oxide as the active part of the cathode.
An object of the invention is to provide a cathode active material for a high voltage secondary battery having an improved performance. In particular, it is an object to provide a cathode active material having better cycle durability.
Embodiments of the invention generally relate to a cathode active material for a secondary battery where the cathode is fully or mainly operated above 4.4 V vs. Li/Li+ and comprise sulfate to improve the cycle durability of the battery. It has been shown, that when the cathode active material comprises sulfur in the form of a sulfate, and not as a sulfide, the discharge capacity at rapid discharges (e.g. at 10 C) increases and the internal resistance and degradation decrease, whilst the discharge capacity of the cathode active material is unchanged.
The term “being fully or mainly operated above 4.4 V vs. Li/Li+” is meant to denote that the battery is intended for operation above 4.4 V vs. Li/Li+, and that this is the case most of the time of use of the secondary battery, such as at least 70% of the time or even 90% of the time.
In an embodiment, the cathode active material comprises lithium. Thus, the cathode active material is a material for a high voltage secondary lithium battery.
In an embodiment the cathode active material has the composition LixMyMn2−yO4−v(SO4)z, where 0.9≤x≤1.1, 0.4≤y≤0.5, 0<z≤0.1, 0≤v≤z and M is a transition metal chosen from the group consisting of Ni, Mg, Ti, V, Cr, Fe, Co, Cu, Zn, Al, Ga, Rb, Ge, Mo, Nb, Zr, Si and combinations thereof, and where the cathode active material comprises sulfate as a discharge capacity fade reducing compound. When the sulfur in the cathode active material is present in the form of sulfate, and not in the form of sulfide, the electrochemical performance of the material is improved. As it will be shown below the chemical composition of the above-mentioned spinel oxide is such that the sulfur is present in the cathode active material as a sulfate. In particular, the degradation rate is diminished compared to a material not comprising the sulfate.
In an embodiment of the invention, the transition metal M of the cathode active material is Ni. Thereby, the composition of the cathode active material becomes LixNiyMn2−yO4−v(SO4)z, where 0.9≤x≤1.1, 0.4≤y≤0.5, 0<z≤0.1, 0≤v≤z. Substituting some of the Mn in the spinel structure with Ni is advantageous due to the electrochemical activity of the Ni2+/Ni4+ redox couple at 4.7 V vs Li/Li+ leading to high capacity above 4.4 V vs Li/Li+. Additional benefits of the incorporation of Ni include lowering the amount of trivalent Mn, which reduces the risk of Mn dissolution in the electrolyte. Furthermore, partial substitution of Mn with Ni is also known to improve cycling behavior as well as rate capability.
In an embodiment of the invention, the bulk structure of the LixMyMn2−yO4−v(SO4)z cathode active material has a spinel structure. The spinel structure is for example described by the Fd-3m space group. Generally, spinel phase has two possible crystallographic forms: the cation ordered spinel phase (space group P4332) and the cation dis-ordered phase (space group Fd-3m). In the ordered phase, Mn4+/Mn3+ and M2+ (e.g. Ni2+) ions occupy distinct crystallographic sites, which gives rise to a superstructure with an easily identifiable X-ray diffraction pattern. In the dis-ordered phase, Mn4+/Mn3+ and Ni2+ ions are randomly distributed. It is well-known to those skilled in the art (see, for example, J. Cabana, et al., Chem. Mater. 2012, 23, 2952) that the degradation (fade) rate of ordered spinel materials is generally higher than that of disordered spinel materials.
It should be noticed that in practice there will often be small deviations from the theoretical composition and average oxidation states when synthesizing a material. This can either be because of deviation from the exact stoichiometry, the existence of defects and inhomogeneity in the structure or the existence of impurity phases which alters the composition of the main phase. It is for instance well known that small amounts of a rock salt phase is present when synthesizing LNMO which affects the stoichiometry of the spinel phase and renders the total material oxygen deficient (Composition-Structure Relationships in the Li-ion Battery Electrode Material LiNi0.5Mn1.5O4, J. Cabana et. al, Chemistry of Materials 2012, 24, 2952). Such unintended deviations should not restrict or in any way limit the scope of the appended claims.
In an embodiment of the invention, the mean primary particle size of the cathode active material is above 50 nm, preferably above 100 nm, and most preferably above 200 nm. Typical sizes are some hundreds nm, but in some cases primary particles of up to 10 or 20 μm are observed. The average primary particle size influences the specific surface area of the cathode active material; smaller particles give rise to a larger specific surface area than larger ones. A lower surface area can improve the cycling stability of the battery, because oxidative decomposition of the electrolyte and metal dissolution from the cathode material, which lowers the stability of the battery, are taking place at the surface of the cathode material.
In an embodiment, d50 of the cathode active material secondary particles is between 1 and 50 μm, preferably between 3 and 25 μm and wherein the particle size distribution of the secondary particles is characterized by the ratio of d90 to d10 of less than 8. Here, d50 is the median value of the volume based particle size distribution; thus, half of the volume of particles has a particle size smaller than d50 and half of the volume of particles has a particle size larger than d50. Similarly, 90 percent of the volume of particles has a size below d90, and 10 percent of the volume of particles has a size below d10. When the particle size distribution is as indicated above, viz. a relatively narrow particle size distribution, it is easier to process the powder into a good battery electrode with a high volumetric content of active material, thereby improving the volumetric energy density of battery.
In an embodiment of the invention, the surface area of the cathode active material is less than 0.5 m2/g, preferably below 0.3 m2/g, and most preferably below 0.2 m2/g. In a secondary battery comprising the cathode active material having a surface area as this, the destructive reaction with the electrolyte of the secondary battery is slowed down as compared to a similar material with a larger surface area.
The crystal growth that takes place to obtain a large average primary particle size will normally also improve the tap density of the material because it is usually associated with sintering that leads to a lower porosity of the secondary particles.
In an embodiment, the tap density of the cathode active material is above 2 g/cm3, preferably above 2.2 g/cm3, and most preferably above 2.35 g/cm3. Typically, the tap density is below 3.0 g/cm3, or even below 2.8 g/cm3. Tap densities above 2 g/cm3 are advantageous since higher tap densities tend to lead to higher active material loading in the electrode of a battery, thus providing higher capacity of the battery.
In an embodiment of the cathode active material according to the invention, the surface of the secondary particles is enriched in sulfate compared to the average composition of the material. Hereby, the total amount of sulfur in the material may be somewhat less than if the sulfate was evenly distributed throughout the material. This entails that the overall weight increase by adding sulfate to the material is less than if the sulfate was evenly distributed throughout the material. The surface layer of the secondary particles is e.g. determined by XPS and the average composition of the material is e.g. determined by ICP.
Another aspect of the invention relates to a secondary battery where the cathode is fully or mainly operated above 4.4 V vs. Li/Li+ comprising the cathode active material according to the invention.
A further aspect of the invention relates to a method for preparing a cathode active material for a high voltage secondary battery having the composition LixMyMn2−yO4−v(SO4)z, where 0.9≤x≤1.1, 0.4≤y≤0.5, 0<z≤0.1, 0≤v≤z and M is a transition metal chosen from the group consisting of Ni, Mg, Ti, V, Cr, Fe, Co, Cu, Zn, Al, Ga, Rb, Ge, Mo, Nb, Zr, Si and combinations thereof, wherein the cathode active material comprises sulfate as a capacity stabilizing compound, the process comprising the steps of:
(a) Mixing and/or co-precipitating starting materials containing metals and sulfur in appropriate molar ratios determined by the molar ratios between metals and sulfate in the final product; and
(b) carrying out heat treatment at a temperature between 700° C. and 1200° C. of the mixture of step (a) to provide the cathode active material.
In the method of the invention, step (a) comprises mixing the relevant starting materials in appropriate molar ratios to end up with the final product after the heat treatment of step (b). The mixing of the relevant starting material may e.g. be mixing and/or co-precipitation of metal carbonate(s), metal hydroxide(s) and/or metal sulfate(s). Additionally, further sulfate(s) may be used in the mixture. The sulfate in the final product may e.g. result from the sulfate(s) and/or from sulfur impurities in the other starting materials. Each of the precursors or starting materials may contain one or more of the metal elements.
The mixing step can involve liquids to aid the mixing of the precursors, if relevant, such as for example ethanol or water.
The term “metal” is meant to denote any of the following elements or combinations thereof: Li and Mn and the transition metal M from the group of Ni, Mg, Ti, V, Cr, Fe, Co, Cu, Zn, Al, Ga, Rb, Ge, Mo, Nb, Zr, Si and combinations thereof.
In an embodiment, step (a) of the method of the invention comprises the sub-steps of:
(a1) mixing and/or co-precipitating starting materials in the form of metal precursors;
(a2) carrying out heat treatment at a temperature between 300° C. and 1200° C. of the mixture of step (a1), resulting in an intermediate, and
(a3) mixing the intermediate of step (a2) with a sulfate precursor to provide the mixture of step (a).
The sub-steps (a1)-(a3) are to be carried out in the order given. In this embodiment, the sulfate precursor is added in step (a3), viz. the first heating step (a2). The final mixture resulting from step (a3) is subsequently calcined in the heat treatment of step (b).
This promotes a shell distribution of the sulfate close to the accessible surface of the secondary particles.
The total sulfur in the cathode active material is detectable, e.g. by energy dispersive X-ray analysis (EDX-analysis) in a SEM-instrument and by inductive coupled plasma analysis (ICP), the latter with a precision of down to ±20 wt ppm.
The chemical identity of the sulfur in the cathode active material (e.g. sulfate or sulfide) is detectable with X-ray Photoelectron Spectroscopy (XPS) by determining the binding energy of the S2p electrons. For metal sulfates the binding energy of the S2p electron is about 169 eV and for metal sulfides the binding energy of the S2p electron is about 161.5 eV. To compensate for charging effect a reference binding energy of 284.8 eV for C1s electrons originating predominantly from the carbon tape is used.
In an embodiment of the method of the invention, the starting materials comprises metal precursors in the form of one or more oxides, one or more hydroxides, one or more carbonates, one or more nitrates, one or more acetates, one or more oxalates or a combination thereof.
In an embodiment, the sulfate precursor comprises a metal sulfate, where the metal is either Li, Ni or Mn or a combination thereof, or the sulfate precursor is a compound comprising SO4 and only leaving SO42− behind in the final product, such as H2SO4 or (NH4)2SO4. In case of (NH4)2SO4, NH4+ is turned into gaseous compounds in the heat treatment of step (b).
In an embodiment of the method of the invention, step (b) is carried out at a temperature of between about 700° C. and about 1200° C. in an oxygen rich atmosphere. Such an oxygen rich atmosphere, which is also denoted “non-reducing atmosphere” or “oxidative atmosphere”, may be e.g. air or a gaseous composition comprising at least 5 vol % oxygen in an inert gas. The non-reducing atmosphere may be provided by the type of gas present within the reaction vessel during heating. Preferably, the non-reducing gas is air.
In an embodiment of the method of the invention, step (a2) is carried out at a temperature of between about 300° C. and about 1200° C. Step (a2) may be carried out in air or in a reducing atmosphere. A reducing atmosphere may be provided by the presence of a reducing gas; for example, the reducing gas may be one or more gases selected from the group of: hydrogen; carbon monoxide; carbon dioxide; nitrogen; less than 15 vol % oxygen in an inert gas; air and hydrogen; air and carbon monoxide; air and methanol; air and carbon dioxide; and mixtures thereof. The term “less than 15 vol % oxygen in an inert gas” is meant to cover the range from 0 vol % oxygen, corresponding to an inert gas without oxygen, up to 15 vol % oxygen in an inert gas. Preferably, the amount of oxygen in the reducing atmosphere is low, such as below 1000 ppm and most preferably below 10 ppm. Typically, oxygen would not be added to the atmosphere; however, oxygen may be formed during the heating.
Additionally, a reducing atmosphere may be obtained by adding a substance to the precursor composition or by adding a gaseous composition to the atmosphere in order to remove all or part of any oxidising species present in the atmosphere of the reaction vessel during heating. The substance may be added to the precursor either during the preparation of the precursor or prior to heat treatment. The substance may be any material that can be oxidised and preferably comprising carbon, for example, the substance may be one or more compounds selected from the group consisting of graphite, acetic acid, carbon black, oxalic acid, wooden fibres and plastic materials.
The heat treatment(s) of step (a3) and/or (b) can be done in one or more steps. In this case, at least one of the steps is carried out at a temperature of above about 700° C. As an example only, a first step is a heat treatment at 900° C. in a given atmosphere, followed by a second step being a heat treatment in the same given atmosphere at e.g. 700° C.
Embodiments of the present invention are explained, by way of example, and with reference to the accompanying drawings. It is to be noted that the appended drawings illustrate only examples of embodiments of this invention and are therefore not to be considered limiting of its scope, for the invention may admit to other equally effective embodiments.
In the following, reference is made to embodiments of the invention. However, it should be understood that the invention is not limited to specific described embodiments. Instead, any combination of the following features and elements, whether related to different embodiments or not, is contemplated to implement and practice the invention.
Moreover, in the following, the terms “cathode active material” is meant to denote a LNMO material with the formula LixNiyMn2−yO4−v(SO4)z, where 0.9≤x≤1.1, 0.4≤y≤0.5, 0<z≤0.1, 0≤v≤z. In addition, the term “cathode active material” is meant to cover reference samples with 0 ppm sulfur corresponding to z=0.
From
From
The relevant amount of S—viz. a sulfur content in the cathode active material is between 1000 and 16000 ppm—is thus an optimization between obtaining good performance as described in
Electrochemical tests have been realized in 2032 type coin cells, using thin composite positive electrodes and metallic lithium negative electrodes (half-cells). The thin composite positive electrodes were prepared by thoroughly mixing 84 wt % of cathode active material (prepared according to Examples 1, 2 and 3) with 8 wt % Super C65 carbon black (Timcal) and 8 wt % PVdF binder (polyvinylidene difluoride, Sigma Aldrich) in NMP (N-methyl-pyrrolidone) to form a slurry. The slurries were spread onto carbon coated aluminum foils using a doctor blade with a 160 μm gap and dried for 2 hours at 80° C. to form films. Electrodes with a diameter of 14 mm and a loading of approximately 7 mg of lithium positive electrode active material were cut from the dried films, pressed in a hydraulic pellet press (diameter 20 mm; 3 tonnes) and subjected to 10 hours drying at 120° C. under vacuum in an argon filled glove box.
Coin cells were assembled in argon filled glove box (<1 ppm O2 and H2O) using two polymer separators (Toray V25EKD and Freudenberg FS2192-11SG) and electrolyte containing 1 molar LiPF6 in EC:DMC (1:1 in weight). Two 250 μm thick lithium disks were used as counter electrodes and the pressure in the cells were regulated with a stainless steel disk spacer and disk spring on the negative electrode side. Electrochemical lithium insertion and extraction was monitored with an automatic cycling data recording system (Maccor) operating in galvanostatic mode.
A standard test was programmed to run the following cycles: 3 cycles 0.2 C/0.2 C (charge/discharge), 3 cycles 0.5 C/0.2 C, 5 cycles 0.5 C/0.5 C, 5 cycles 0.5 C/1 C, 5 cycles 0.5 C/2 C, 5 cycles 0.5 C/5 C, 5 cycles 0.5 C/10 C, and then 0.5 C/1 C cycles with a 0.2 C/0.2 C cycle every 20th cycle. C-rates were calculated based on the theoretical specific discharge capacity of the material of 148 mAhg−1 so that e.g. 0.2 C corresponds to 29.6 mAg−1 and 10 C corresponds to 1.48 Ag−1.
The performance parameter “discharge capacity”, “power capability”, “0.2 C degradation” and “1 C degradation” are extracted from the standard test in the following way. The discharge capacity is the initial discharge capacity at 0.5 C, measured in cycle 7. The power capability is the relative decrease in the measured discharge capacity at 10 C compared to 0.5 C, measured at cycles 29 and 7 respectively. The 0.2 C degradation is the relative loss of discharge capacity at 0.2 C over 100 cycles, measured between cycles 32 and 132. The 1 C degradation is the relative loss of discharge capacity at 1 C over 100 cycles, measured between cycles 33 and 133.
Precursors in the form of 1162.47 g co-precipitated Ni,Mn-carbonate (Ni:0.5, Mn: 1.5) and 190.65 g Li2CO3 are mixed with ethanol to form a viscous slurry. The slurry is shaken in a paint shaker for 3 min. in order to obtain full de-agglomeration and mixing of the particulate materials. The slurry is poured into trays and left to dry at 80° C. The dried material is further de-agglomerated by shaking in a paint shaker for 1 min. in order to obtain a free flowing homogeneous powder mix.
The powder mix is sintered in a muffle furnace 2.5 hours at 700° C. with nitrogen flow.
This product is de-agglomerated by shaking for 6 min. in a paint shaker and passed through a 45 micron sieve. The powder is distributed in a 10-25 mm layer in alumina crucibles and sintered in air 14 hours at 900° C. and 4 hours at 700° C.
The powder is again de-agglomerated by shaking for 6 min in a paint shaker and passed through a 45 micron sieve resulting in 866 g cathode active material consisting of 95.4% LNMO, 3.6% 03 and 1.1% Rock salt.
Three 50 g portions are taken from the produced cathode active material. Two are mixed with 0.3434 g and 0.6868 g Li2SO4, respectively, to obtain sulfur content in the final product of 2000 ppm and 4000 ppm. The mixing is performed by solution of Li2SO4 in 10 g H2O and 8 g ethanol and mixing this with the cathode material. The three powder samples, including the powder without sulfur doping, are sintered 4 hours at 900° C. and 4 h at 700° C. in air. The powder is again de-agglomerated by shaking for 6 min in a paint shaker and passed through a 38 micron sieve. The phase purity of all samples are 95 wt % or above. The electrochemical performances of the three samples are compared in
The actual sulfur contents in the products corresponding to 0 ppm sulfur and 2000 ppm sulfur was determined to be 40 ppm and 2090 ppm, respectively, using ICP.
Precursors in the form of 2258.66 g co-precipitated Ni,Mn-carbonate (Ni:0.5, Mn: 1.5) and 394.78 g LiOH are dry-mixed for 1 hour.
Two portions of 50 g are taken from the dry-mixed precursor: One is mixed with Li2SO4 to obtain sulfur content in the final product of 2000 ppm. The two powder portions are sintered in a muffle furnace 3 hours at 700° C. with nitrogen flow.
The products are de-agglomerated by shaking for 6 min. in a paint shaker and passed through a 45 micron sieve. The powder is distributed in a 10-25 mm layer in alumina crucibles and sintered in air 14 hours at 900° C. and 2 hours at 700° C.
The powder is again de-agglomerated by shaking for 6 min in a paint shaker and passed through a 45 micron sieve. The phase purity of both samples are 95 wt % or above. The electrochemical performances of the two samples are compared in
To determine the chemical identity of the sulfur at the surface, XPS measurements were conducted on the cathode active materials with 2000 ppm sulfur doping from Examples 1 and 2.
The XPS measurement can also reveal any radial distribution of the sulfate in the cathode active material particles. Table 1 shows the relative atomic ratios of the relevant compounds O, Mn, Ni and S in the cathode active materials from Examples 1 and 2 containing 2000 ppm sulfur.
O/(Mn+Ni) is the atomic ratio between oxygen and the transition metals in the LNMO spinel, i.e. Mn and Ni. The bulk value of this is 2, but deviations from bulk values are often found at the surface. (Mn+Ni)/S is the atomic ratio between the transition metals in the LNMO spinel and sulfur. This is used to calculate the value of z in the surface, zsurface. by using the formula LixMyMn2−yO4−v(SO4)z. A calculation of the relative amount of sulfur by weight corresponding to the z-value shows that the sulfur content is 10 times higher than the bulk value when the material is prepared as described in Example 1, and 3 times higher than the bulk value when the material is prepared as described in Example 2. This shows that the sulfate is preferentially found in the surface of the particles, when either one of the methods described in Examples 1 or 2 are used.
Two cathode active materials based on precursors with different sulfur impurity levels in the Ni,Mn-carbonate are prepared identically: Precursors in the form of 30 g co-precipitated Ni,Mn-carbonate (Ni:0.5, Mn: 1.5) and 5.1 g LiOH are mixed dry in order to obtain a free flowing homogeneous powder mix. The two powder mixes are sintered in a muffle furnace 3 hours at 730° C. with nitrogen flow.
The products are de-agglomerated by shaking for 6 min. in a paint shaker and passed through a 45 micron sieve. The powder is distributed in a 10-25 mm layer in alumina crucibles and sintered in air 4 hours at 900° C. and 12 hours at 715° C.
The powders are again de-agglomerated by shaking for 6 min in a paint shaker and passed through a 20 micron sieve. The phase purity of both samples is 98 wt %. The electrochemical performances of the two samples are compared in
The two precursors have different amounts of sulfur impurities. One is 100 ppm and the other is 500 ppm. It was shown by ICP that the sulfur to Ni—Mn ratio is constant throughout the entire preparation of the sulfate doped cathode active material such that different amounts of sulfur impurities in the precursor will give battery cathode materials with correspondingly different amounts of sulfate doping.
Comparison of the electrochemical performance of the cathode materials produced in Examples 1, 2 and 3 is shown in
While the invention has been illustrated by a description of various embodiments and while these embodiments have been described in considerable detail, it is not the intention of the applicant to restrict or in any way limit the scope of the appended claims to such detail. Additional advantages and modifications will readily appear to those skilled in the art. The invention in its broader aspects is therefore not limited to the specific details, representative methods, and illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the spirit or scope of applicant's general inventive concept.
| Number | Date | Country | Kind |
|---|---|---|---|
| PA 2016 00490 | Aug 2016 | DK | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2017/071009 | 8/21/2017 | WO | 00 |
