WO2012107313A1 - High nickel cathode material having low soluble base content - Google Patents
High nickel cathode material having low soluble base content Download PDFInfo
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- WO2012107313A1 WO2012107313A1 PCT/EP2012/051492 EP2012051492W WO2012107313A1 WO 2012107313 A1 WO2012107313 A1 WO 2012107313A1 EP 2012051492 W EP2012051492 W EP 2012051492W WO 2012107313 A1 WO2012107313 A1 WO 2012107313A1
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
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- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C01P2002/54—Solid solutions containing elements as dopants one element only
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
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- H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Definitions
- the invention relates to cathode materials for Li-ion batteries in the quaternary phase diagram Li[Lii /3 Mn 2 /3]0 2 - LiMn 1 /2 Ni 1 /2 0 2 - LiNi0 2 - LiCo0 2 , and having a high nickel content. Also a method to manufacture these materials is disclosed.
- LiCo0 2 (or "LCO") was the dominating cathode material for rechargeable lithium batteries.
- LCO has a relatively high capacity (150 - 160 mAh/g at 3 - 4.3V) together with a high density (true density about 5.05 g/cm 3 ) and is relatively easy to be produced with good quality. It has a relative high Li diffusion so it is possibly to utilize larger, dense particles (10 - 20 ⁇ size) with small surface area (0.1 - 0.5 m 2 /g). These large, dense, low surface area particles can easily be prepared with a small amount of soluble surface base - as will be defined in more detail below. All in all commercial LCO is a robust and easy to manufacture cathode powder.
- LCO is also a "friendly" material during battery production. It is easily processed by battery producer (slurry making, coating, compacting of electrodes, ). It allows to obtain electrodes of low porosity thus more powder can fit into the confined space of a battery horrtively resulting in a high energy density. For a long time these nice properties ensured the dominance of LiCo0 2 for rechargeable lithium batteries for portable applications. LCO however also has serious drawbacks. A main drawback is the relative scarcity of Co resources related to it is the relatively high cost of cobalt metal. Still worse, historically the cobalt prize shows wild fluctuations, and these fluctuations possibly increased the need to find substitutes for LiCo0 2 .
- Lithium - nickel- manganese -cobalt- oxide The main substitute for LCO, which has emerged commercially within the last 5 or so years, is Lithium - nickel- manganese -cobalt- oxide.
- This material belongs to the quaternary phase diagram Li[Lii/3Mn2/3]0 2 - LiMn ⁇ Ni ⁇ C ⁇ - LiNi0 2 - LiCo0 2 . Additionally this composition can be modified by doping. It is known for example, that elements like Al, Mg, and sometimes Zr can replace Co, Ni or Mn.
- Within the complex quaternary phase diagram there is a wide degree of freedom to prepare electrochemically active phases with different composition and quite different performance.
- special precursors such as mixed transition metal hydroxides need to be used. The reason is that high
- the cathode precursors need to contain the transition metal in a well-mixed form (on atomic level) as provided in mixed transition metal hydroxides, carbonates etc..
- transition metal hydroxides When mixed transition metal hydroxides are used as precursors, they are obtained by co-precipitating transition metal sulphates and technical grade bases like NaOH, which is amongst the cheapest industrial route for Li-M-0 2 precursor preparation.
- This base contains C0 3 2" anions in the form of Na 2 C0 3 , which are subsequently trapped in the mixed hydroxide - the mixed hydroxide typically containing between 0.1 and 1 wt of C0 3 2" .
- the lithium precursor Li 2 C0 3 or a technical grade LiOH*H 2 0, often containing at least 1wt of Li 2 C0 3 is used.
- high nickel cathodes "LNO " like LiNio. 8 Coo.
- Li 2 C0 2 when the lithium hydroxide and transition metal precursors are reacted at high temperature, typically above 700° C, the Li 2 C0 3 impurity remains in the resulting lithium transition metal oxide powder, especially on its surface.
- higher purity materials are used, less Li 2 C0 3 impurity is found, but there is always some LiOH impurity that reacts with C0 2 in the air to form Li 2 C0 3 .
- the use of high purity materials is proposed in JP2003-142093, however such expensive precursors are not preferred.
- the cathodes in this diagram can have the general formula
- Li a ((Ni z (Ni1 ⁇ 2 Mn 1 ⁇ 2 )y Co x ) 1 . k Ak) 2 -a 0 2 , wherein x+y+z 1 , and A is a dopant, with 0 ⁇ k ⁇ 0.1 , and 0,95 ⁇ a ⁇ 1 .05.
- the values of x,y,z correspond to the above described values of X, Y and Z respectively.
- NCA e.g. LiN1O.8Coo.15Alo.05O;>
- 111 e.g. Li 1 .05AA0.95O2 with or "532”
- NCA for example, has a very high capacity, by far exceeding LiCo0 2 . But it is very difficult to prepare since C0 3 free precursors - like purified LiOH - are needed, and a C0 2 free reaction atmosphere -like oxygen - and the final cathode material is sensitive to moisture exposure. It is unstable during long air exposure and it typically has a very high content of soluble base.
- the content of soluble base obtained for a given cathode powder can be determined in a reproducible manner by pH titration, which depends on parameters such as the total soaking time of powder in water.
- Bases are originating mainly from two sources: first, impurities such as Li 2 C0 3 and LiOH present in the Li-M-0 2 ; second, bases originating from ion exchange at the powder surface:
- LiCo0 2 An essential requirement to successfully replace LiCo0 2 is a cheap and simple production process.
- - lithium carbonate is used and the firing is done in normal air.
- Z there is a strong trend to increase "Z" thus pushing the energy density further up.
- the current art however teaches that there is a limit to increase Z using such a process: in US2006/0233696 for example it is said that, for Z>0.35, the doped LiNi0 2 cannot be prepared in air on a large scale and U2CO 3 cannot be used as a precursor. That is because this document believes that a good Ni-based lithium transition metal oxide can only be obtained when it is substantially free of soluble bases.
- SBC soluble base content
- SBC soluble base content
- SBC soluble base content
- the surface of the lithium transition metal oxide powder is free of both lithium carbonate and LiOH phase impurities.
- the powders are not coated.
- the values in these embodiments for (SBC- Li 2 C0 3 ) on the one hand, and (SBC-Li 2 C0 3 )/ (SBC-LiOH) on the other hand, are typically obtained when technical precursor materials are used that contain a lot of C0 3 2" type impurity.
- lithium transition metal oxide powder When the lithium transition metal oxide powder is not sintered under air - but eg under oxygen - or when high purity precursors are used, like pure LiOH, then (SBC-Li 2 CO 3 ) ⁇ 0.085 wt , and/or (SBC-Li 2 C0 3 )/ (SBC-LiOH) ⁇ 0.2, but this practice results in a much higher cost of manufacturing, and, as will be shown below, it results in a lower material performance for "High Z" materials.
- the lithium transition metal oxide powders formula: 0.40 ⁇ z ⁇ 0.45.
- the lithium transition metal oxide powder has a BET value between 0.22 and 0.40 m 2 /g , and a SBC between 80 and 120 ⁇ /g, corresponding to the equilibrium SBC value (SBC e ) powders with 0.40 ⁇ z ⁇ 0.45. These values can provide excellent performances.
- the lithium transition metal oxide powder has a surface specific SBC between 80 and 125 ⁇ /m 2 , the surface specific SBC being the ratio between SBC and BET surface area, the BET surface area being measured after washing and drying.
- the dopant A can be Al, Ti or Mg. Al can be doped up to 10 mol , whilst Ti and Mg are, according to another embodiment, limited to 5 mol .
- the dopant can be B, Ca, Mn, Cr, V, Fe, Zr, S, F, P or Bi. Their content may be limited to 1 mol .
- the invention discloses uncoated Li-nickel-manganese-cobalt-oxides used as cathode in Li rechargeable batteries with higher capacity obtained by a larger content of nickel.
- High nickel cathodes typically contain LiOH and Li 2 C0 3 impurities.
- the current invention can provide high nickel cathodes free of impurities, and in one embodiment with a content of soluble base near to or at the equilibrium value of about 80 - 120 ⁇ /g.
- the positive electrode material of the invention is a certain equilibrium base content, not zero, but less than a cathode material which has a Li 2 C0 3 , LiOH or Li 2 0 impurity. It will be explained in more detail below that the concept of soluble base is a surface property rather than an impurity.
- the current invention can provide for novel cathode materials which contain the correct amount of soluble base, which base furthermore does not originate from impurities.
- a lithium transition metal oxide powder has the equilibrium soluble base content SBC e , its initial soluble base content SBC, is determined as described in Example 2.
- a sample of the powder is re-heated under air at a temperature T of at least 500° C, and less than the temperature where the morphology of the powder starts to change by sintering (which is easy to check using SEM), during a time t of typically 5 to 10 hrs under air, and for the re-heated sample the soluble base content SBC d is determined. If the difference between SBC d and SBC, is less than 10% of SBC, the powder has the equilibrium soluble base content SBC e .
- the re-sintering temperature is set at 790° C, and t is 10 hr.
- US7,648,693 describes a cathode material with a low content of soluble base.
- the patent only discloses relatively small values of Z (Z ⁇ 0.35), contrary to the present invention.
- This document however is silent about the need to provide high Ni materials with a soluble base content close to or at the equilibrium soluble base value.
- WO2009- 021651 discloses cathode materials that are obtained after washing or washing and reheating. These materials contain a too small amount of soluble base, being less than the equilibrium value.
- the invention discloses cathode materials with a selective range for Z, and containing a certain amount of soluble base that is higher than in washed (and reheated) cathode materials, and near to or at the equilibrium value.
- the invention can provide a method for preparing the powderous lithium transition metal oxide described above, comprising the steps of:
- transition metal precursor prepared from the co-precipitation of transition metal sulphates with a base
- lithium precursor selected from the group consisting of technical grade LiOH*H 2 0 containing a carbonate impurity, and U2CO 3 ;
- the transition metal precursor is obtained by co-precipitating transition metal sulphates and technical grade bases like NaOH.
- the sintering step is preceded by a heating step of at least 5 hrs at a temperature of at least 650° C and less than 800° C, under a forced flow of air of at least 2 m 3 /kg mixture.
- the transition metal precursor is a mixed hydroxide containing between 0.1 and 1 .0 wt CO3 2" .
- the lithium precursor is a technical grade LiOH*H 2 0 containing at least 1wt of Li 2 C0 3 .
- This method can provide a cheap way of making air stable lithium transition metal oxide powders using cheap precursors that contain carbonate impurities, which method is performed under air (containing C0 2 ) instead of using an expensive pure oxygen atmosphere.
- a research schedule can be developed comprising the steps of:
- step (e) If in step (e) the condition (SBC d - SBC b ) ⁇ (0.1* SBC d ) is fulfilled the parameters T b , t b , D b can be retained for the sintering step in the preparation of the lithium transition metal oxide and the process according to the invention is achieved, or in case that new parameters had to be set during the repetition step (or steps), the final parameters T r , t r and D r are the values to be used in the process according to the invention.
- the transition metal precursor is a mixed Ni-Mn-Co hydroxide or oxyhydroxide.
- the mixed Ni-Mn-Co hydroxide or oxyhydroxide further comprises dopant A.
- T b is at least 900° C, and step (d) is performed at a temperature between T b -120 and T b -80° C.
- Figure 1 Applied temperature profile and obtained C0 2 profile during firing reaction of precursor blend with different compositions in a flow of air.
- Figure 2 Typical pH titration profile.
- Figure 3 Typical commercial product morphology.
- Figure 4a (left panel): Upper and lower capacity range for "commercial” morphology samples as function of "Z”.
- Figure 4b (right panel): Typical upper and lower value for the equilibrium SBC as a function of capacity.
- FIG 5a Coin cell testing of sample S1 (non washed)
- Figure 5b Coin cell testing of sample S2 (washed & dried at 200°C)
- Figure 6 Electrochemical testing of a LiM0 2 sample (S6.2) prepared in the pilot plant using (1 ) a large sintering time (> 24h) and (2) a high air flow (total: 2 m 3 /kg of blend)
- Figure 7.1 total SBC as function of stirring time ( ⁇ /g vs. sq. root of time)
- Figure 7.2 LiOH and Li 2 C0 3 fraction of the SBC as function of stirring time (wt vs. sq. root of time)
- the current invention is related to a better understanding of the phenomenon which we call "soluble base content", which will be referred to as "SBC” in the following.
- SBC soluble base content
- the SBC is relatively stable for low Z like "111 ", SBC increases a relatively short time and then stabilizes for intermediary Z like "532" and SBC continuously increases in the case of high Z like "NCA”.
- the measured SBC is the result of a reaction of the surface of the particles with water. In fact, the water changes the surface. Adsorbed molecules might dissolve and create soluble base which contributes to the SBC. For example Li-0 bonds on the surface might be replaced by OH bonds and create dissolved LiOH base. Li-C-0 bonds might dissolve to create Li 2 C0 3 base. A further contribution to the SBC is an ion exchange ("IX”) mechanism. If Z is not too large then Li in the bulk does not react with water.
- IX ion exchange
- slurry stability means that the viscosity does not change dramatically during coating. In a worst case scenario “gelation” of the slurry can occur, making the coating impossible. A good slurry stability also means that the quality of the dispersion of cathode powder, conductive additives, etc. in the binder solution does not change. In a worst case scenario flocculation can occur, causing carbon-carbon and/or cathode-cathode agglomeration. It was observed that high SBC tends to cause a poor slurry stability. Especially undesired is a large LiOH type fraction of the SBC.
- the cathode contains high SBC then the high temperature performance of batteries is influenced. During high temperature exposure of charged batteries gas evolves. In the case of prismatic and polymer cells this gas evolution is highly
- washing will simply remove the impurity. After washing, measurement of SBC gives negligible values. But the approach fails because SBC is not an impurity but a surface property. During washing, first, adsorbed surface molecules are dissolved or modified. Secondly an IX proceeds until a certain level of saturation. Near to the surface this results in protons being present instead of Li cations. We observed that washed and reheated cathodes have poor electrochemical performances. Possibly protons are still present, which causes poor performances in real cells. An improved washing process includes the re-heating of the cathode in order to remove the protons. These protons that are removed by reheating need to be replaced by something else, since the layered phases usually do not tolerate cationic vacancies.
- Li 2 C0 3 As lithium precursor, Li 2 C0 3 has the following advantages: (1 ) its low price, (2) its non-hydroscopic character and (3) its high melting point. Most of the Li 2 C0 3 reacts with the metal precursor (such as a mixed nickel-manganese-cobalt hydroxide) before the temperature reaches the Li 2 C0 3 melting point. There is less tendency for de- mixing due to a flow-down effect. If unreacted Li 2 C0 3 remains in the final cathode a high SBC value is measured. Furthermore a poor slurry stability and excessive bulging of the battery is observed. Poorly prepared cathode materials have a high SBC (higher than the equilibrium value SBC e ) which originates from unreacted lithium precursor. To increase the completeness of reaction the following actions can be envisaged:
- the current invention can provide cathode materials that are free of LiOH, Li 2 C0 3 , and LiOH * H 2 0 impurities (in the sense of comprising a secondary impurity phase), and having an SBC near to the equilibrium value SBC e .
- Example 1 reaction kinetics for different "Z" values.
- the morphology of the precursors is quite similar: they have 8-10 ⁇ sized spherical particles with a tap density of about 2 g/cm 3 .
- These precursors are well mixed with appropriate amounts of Li 2 C0 3 , so as to obtain the following Li:M blend ratios: M1 ) 1 .1 : 1 , M2) 1 .01 : 1 , M3) 1 .01 : 1 .
- Trays of approx. 23 x 23 x 8cm size are filled with 1 kg of the blends.
- the blend occupies about 50% of the tray volume.
- the trays are heated in a laboratory chamber furnace in a flow of air (20 L/min) .
- the surrounding gas has a partial pressure that is lower than the C0 2 equilibrium partial pressure for the corresponding composition.
- the equilibrium pressure generally decreases with increasing Ni:Mn.
- the C0 2 pressure is high.
- the lithiation reaction proceeds the Li:M in the crystal structure increases and the equilibrium C0 2 partial pressure decreases.
- the lithiation reaction can only finish if the gas flow has effectively removes the evolved C0 2 .
- the lower the equilibrium C0 2 partial pressure the less C0 2 can be removed by the gas flow. It can be concluded that with small Z the reaction proceeds fast. As Z increases the reaction rate decreases and approaches the zero rate slower and slower. Obviously it becomes increasingly difficult to finish reaction (1 ) to 100%. If the reaction is not fully finished then unreacted Li 2 C0 3 remains.
- the unreacted Li 2 C0 3 causes a high value of SBC.
- the SBC is caused by the presence of a surface impurity. If the reaction is fully finished then no unreacted Li 2 C0 3 is present and the SBC is related to the surface property and not to an impurity.
- Example 2 measurement of SBC of a sample LiM0 2 This Example demonstrates a possible method to measure SBC: a pH titration at constant flow. In the following Examples (3-9) this method is used to measure the SBC.
- Dl de-ionized
- V1 , V2 ml of acid at inflection point 1 , 2 (V2>V1 );
- Figure 2.1 shows a typical pH titration profile (the material measured being sample S8B of Example 8 below). The top figure shows the pH as function of acid addition ( unit : ⁇ of acid per g of cathode), the bottom figure shows the derivative of the pH profile to show the inflection points V1 and V2.
- MOOH transition metal oxyhydroxide precursor
- the morphology is spherical with a tap density of approx. 2.2 g/cm 3 .
- the D50 of the article size distribution is about 10 ⁇ .
- the precursor is mixed with appropriate amounts of Li 2 C0 3 .
- the Li : M stoichiometric blend ratios for 4 different samples is listed in Table 1 . 200 grams of the blend is filled in trays. 2 trays are simulatenously fired. The dwell temperature is 900° C.
- Samples cooked for 12 hours have a 2 - 4 times higher SBC value than samples cooked for 24 hours (which are near to the equilibrium SBC).
- the SBC of the 12 hour cooked samples contains a large fraction of base caused by remaining unreacted Li 2 C0 3 whereas the SBC of the 24h cooked samples mostly originates from surface properties. For example, when the 24 h samples are grinded and recooked again the SBC does not decrease much further.
- Typical equilibrium values SBC e for a typical commercial morphology increases from about 15-20 to 50-70 to 100 -150 ⁇ /g (base per g of cathode). At the same time the reversible discharge capacity increases from 160 170 180 mAh/g.
- Example 4 SBC e value as a function of Z.
- Higher values of Z can practically not be prepared in air (which contains natural C0 2 ) using Li 2 C0 3 as precursor.
- Table 2 lists the typical values (upper and lower limit ) for the equilibrium SBC e , and the capacity of the materials.
- the table lists a low value obtained for larger and dense particles (typical BET 0.25 - 0.3 m 2 /g) with a lower Li:M ratio and relatively large crystallites (up to 1 ⁇ ), whereas the high value refers to smaller particles with some remaining porosity (typical BET: 0.3 - 0.6 m 2 /g) with a higher Li:M ratio and relatively small crystallites.
- Table 2 also lists a range for the capacity where the lower value is obtained for larger and dense particles.
- Figure 4a shows the upper and lower capacity range (mAh/g) for
- Example 5 achieving a low SBC value by washing and reheating.
- a precursor with composition MOOH is received from the precipitation pilot plant.
- the precursor is blended with Li 2 C0 3 resulting in a 2.5 kg blend.
- 2 identical samples of each about 2 kg are prepared using a chamber furnace.
- the air flow rate is 25 L/min.
- the sinter temperature is 930° C.
- the sample has a Li:M blend ratio of 1 .062.
- a relatively low sinter temperature and a relatively high Li:M ratio are chosen to achieve a high cycle stability at fast rate. From this precursor a washed sample is prepared, that needs to be dried. Different drying (or reheating)
- temperatures are tested by reheating the washed sample in air for 5h. 2 series of final samples are prepared. For the first series reheating is performed at 200 and 400°C. To confirm the cycle stability results the series are repeated at 300, 400 and 500° C.
- the samples are investigated by BET surface area measurement, pH titration to obtain the SBC value and by special coin cell testing to investigate the cycle stability at fast rate (1 C charge / 1 C discharge) and high voltage (3.0 - 4.5V).
- the high voltage - high rate testing is believed to give representative results for commercial cells.
- Table 3 summarizes the obtained results.
- the fade rate is obtained after 53 cycles fast cycling (all cycles at 1 C charge / 1 C discharge, except 1 st cycle: at C/10) at high voltage
- the equilibrium value SBC e for sample S1 is relatively high because of 2 reasons. First the relatively high Li:M ratio and second a large inner surface. The large inner surface - manifested by the large BET after wash - takes part in the surface base reactions. It is caused by the relatively low sintering temperature. The pristine sample (without wash) has a lower surface area because parts of the inner porosity are closed by soluble salt like Li 2 S0 4 which originate from the typical sulfate impurity (about 0.3 mol ) of the MOOH precursor. For the equilibrium value SBC e the total surface (as measured after wash) and not the pristine BET is relevant.
- Figure 5a shows the coin cell testing results of the sample S1 (non washed), whilst Figure 5b shows the coin cell testing of the sample S2 (washed & dried at 200° C) .
- the left figure shows the charge and discharge curves for the 1 st cycle, at C/10 (converging lines at top right at 4.5 V), and 3 discharge curves at cycles 4, 23 and 53, each at 1 C. (from right to left).
- the rate for 1 C is 160 mA/g (in 1 hr).
- the right figure shows the fade: obtained capacity against cycle number (Cy).
- the small dots are for the charge, the bigger dots for the discharge.
- Example 6 Production of high Z materials with SBC values near to the equilibrium.
- This example illustrates how cathode materials with relatively high Z can be produced at industrial scale. Important preconditions are to (1 ) supply enough air , (2) use a sufficient long reaction time and (3) use a high enough reaction temperature. Two different mixed transition metal oxyhydroxide precursors with composition MOOH, are obtained from a precipitation pilot plant.
- the precursors are mixed with appropriate amounts of Li 2 C0 3 using a Li:M molar ratio of 1 .01 and 1 .03.
- the blend is filled into trays (1 .5 kg blend in each tray) which are fed into a tunnel type continuous roller kiln pilot furnace at a rate of 2 trays per 3 hours.
- the temperature is 880° C
- the total dwell time is 25 hours, starting with a 5h dwell at 700° C followed by a 20h dwell at 880° C.
- Air is continuously pumped into the heating and dwell zone of the furnace at a rate of 6 m 3 /h. This corresponds to a total air volume of 6 m 3 /kg blend during heating and dwell.
- the SBC is about 110 ⁇ / g of cathode. Table 4 lists the obtained results.
- the air flow can be utilized more efficiently, so that it is estimated that about 2 m 3 / kg of blend and at least 18 hours reaction time (heating + dwell) are needed to complete the reaction.
- the reaction can be split into 2 parts. First the blend is precooked to achieve a poorly reacted LiM0 2 . Then precooked LiM0 2 is sintered. Under these conditions the requirements for air flow and sinter time are slightly lower, it is estimated that at least 1 m 3 air and 12 h are needed during the sintering to complete the second reaction.
- the term "complete the reaction” refers to a cathode product which is free of base impurity second phases (free of unreacted Li 2 C0 3 and LiOH, and LiOH*H 2 0 formed during the cooking). Under these conditions the SBC is near to the equilibrium value SBC e .
- a sample S7A is prepared in a continuous pilot plant furnace under given conditions. These conditions refer to the used precursors, the Li:M blend ratio, the airflow, and the dwell time and temperature.
- the sample obtained after the test cook is called S7B.
- the reheating occurs in air at a temperature at least 50° C but not more than 200° C lower than the sintering
- sample S7A and S7B are within 10%. Thus the reaction practically is finished after the 1 st cook.
- the different ratio between LiOH and Li 2 C0 3 type base is related to details of the cooling: sample S7A was cooled in the pilot furnace, whereas sample S7B, after reheating in a box furnace, was cooled in that box furnace.
- the equilibrium SBC is considered not achieved, and the conditions for preparing the lithium transition metal oxide powder have to be changed by increasing either one, two or all of the following process properties: reaction time, reaction temperature, effective air flow.
- An iteration can be started until the conditions have been determined wherein the SBC after test cook is within 10% of the value before the test cook.
- the value after the test cook can be considered to be the equilibrium SBC e .
- the surface specific equilibrium value of SBC for the given composition can be obtained by measuring the BET surface after a wash. The surface specific equilibrium value of SBCe is then the equilibrium SBC e (expressed in ⁇ /g) divided by the surface area (m 2 /g) after wash.
- the obtained value ( ⁇ /m 2 ) is, for sufficient high temperature, relatively independent of the morphology.
- it is a material property, defined by the composition of the material.
- the BET after wash of sample S7A is 0.615 m 2 /g.
- the surface specific equilibrium SBC e is about 146 ⁇ /m 2 .
- Example 8 SBC as a material property. This example demonstrates that the SBC is related to the property of the material to create base if in contact with water, instead of creating a separate impurity phase. If the SBC originates from an impurity phase - for example residual unreacted Li 2 C0 3 or LiOH, then we expect the following behaviour:
- the SBC should not depend on the water to cathode ratio as long as the solubility limit is not reached.
- sample S7A of example 7 we use sample S7A of example 7.
- the sample is LiM0 2 with
- Table 6 and Figures 7.1 and 7.2 show the evolution of the different SBC values as a function of stirring time.
- Fig. 7.1 gives the total base (bottom line: values between brackets)
- Fig. 7.2 gives the values for SBC-Li 2 C0 3 (stars) and SBC-LiOH (pentangles), test measurements and repeated measurements are connected by a line.
- Table 7 and Figure 8 show the evolution of the total SBC as a function of water to cathode mass.
- the bottom line gives the values between brackets of the repeated experiments in Table 7.
- the LiOH and Li 2 C0 3 fractions are obtained using the procedure described in Example 2.
- Table 6 and Figure 7.2 show that the LiOH type base increases whereas the Li 2 C0 3 type remains roughly stable.
- the initial increase of LiOH type base follows a square-root of the time (in minutes) dependency, which is typical for diffusion limitation (which is expected for an IX reaction.)
- the gradual increase of LiOH type base is believed to originate from the ion exchange reaction between protons in water and lithium cations in the upper atomic layers of the cathode.
- Table 7 shows the results of varying the water to cathode ratio.
- the effect of more water is that the Li in solution is more diluted, causing a lower pH. This decreases the Li chemical potential in the solution compared to the Li chemical potential in the bulk. As a result the driving force for the ion exchange reaction increases, this speeds up the IX reaction and also allows that deeper located layers of lithium can take part.
- the surface specific SBC value was defined as SBC ( ⁇ /g) divided by the BET surface area after wash (m 2 /g).
- SBC surface specific SBC
- a sample lithium transition metal cathode materials LiM0 2 with is prepared from a blend of mixed hydroxide precursor MOOH and Li 2 C0 3 having a Li:M stoichiometric ratio of 1 .03.
- the blend is fired at 890°C in air for 24h, using a high flow of air in a pilot plant furnace, and several kg are prepared.
- the pH titration test shows a SBC of 97 ⁇ /g. This value is near to the equilibrium value for the given morphology and composition, in line with the results obtained in Ex. 6.
- Small material samples (size: about 50g) are reheated in a chamber furnace using a high air flow rate.
- the BET surface area and the SBC of the treated samples is measured.
- the reheating temperature is above the sintering temperature, sintering is expected, and an increase of crystallite size is observed.
- the SBC decreases because the composition does not change but the true surface area decreases.
- a good measure of the true surface area is the BET surface area obtained from washed and reheated samples.
- the BET surface area after wash had good reproducibility, it does not strongly depend on the water to solid ratio during washing or the stirring time.
- the BET after wash is obtained as follows: 7.5g powder samples are immersed in 70 ml of water and are stirred for 5 min, followed by filtering and drying at 150°C. Table 8 shows the preparation conditions and obtained results.
- the area specific value of SBC is approximated by the slope of the linear fit (dot-dot- dash line) in the graph. It is estimated to be about 100 ⁇ /m 2 .
- the above shows that we can define the surface specific SBC as: SBC (in ⁇ /g) divided by the true BET (m 2 /g) where the BET is obtained after washing and drying. Using the data in Table 8 yields 110 ⁇ /m 2 for sample S9.
- the values of the specific surface SBC calculated from S9B to S9E are within 10% of this value.
- the "z" value is 0.44. This specific surface SBC value can be compared with approx.
Abstract
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