Patent Application
20220263085
The present invention generally relates to a novel sodium layered oxide compound, to a device incorporating said compound such as an electrode comprising said sodium layered oxide compound, or in an electrochemical energy storage cell or device for example a Na-ion battery. It further relates to a method to manufacture and/or to use such a compound and devices incorporating them.
Sodium ion (Na-ion) batteries are growing rapidly as a potential energy storage technology for applications in which cost rather than weight and/or energy density of the cell is a determining factor.
Several prototypes of sodium ion batteries, using polyanionic compounds (e.g. Na3V2(PO4)2F3, named hereafter NVPF) as a positive electrode material, have been proposed. The results have been acceptable but the use of a rare and toxic element such as vanadium has undesirable environmental consequences.
Alternative compounds have been investigated such as layered sodium transition(s) metal oxides (e.g. NaxMO2, wherein x can be up to 1, and M is at least one transition metal ion(s)). NaxMO2 could be stabilized in different layered stacking according to the amount x of sodium it contains. For example, NaxMO2 is an O3-type layered oxide when x is about 1 and can be a P2, P3-type layered oxide when x is below or equal to 0.8 (see refs. 1, 2). In the used nomenclature such as O3, P2, P3, the letter O or P represents respectively the sodium in octahedral (O) or prismatic (P) site and the number represents the number of MO2 layers in the unit cell, the smallest repeating unit having the full symmetry of the crystal structure (ref. 3).
NaxMO2 has a lower molecular weight than NVPF. Therefore, theoretical higher values of specific capacity and specific energy at a given voltage range were expected for sodium layered oxides, compared to NVPF compounds (refs. 4, 5).
However, the sodium layered oxides reported so far have shown poorer capacity retention than NVPF over hundreds of cycles. (refs. 6, 7). In fact, the sodium layered oxides undergo a volume shrinkage and/or swelling due to several phase transitions. As a matter of fact, hardly 50% of the theoretical capacity is achieved with O3—NaxMO2 as the material suffers with continuous phase transition during cycling, especially in the extended voltage range, i.e. a voltage higher than 4.0 V vs. Na+/Na (refs. 6, 9). The P2 and P3 sodium layered oxides NaxMO2, having less than one sodium per transition metal ion showed limited capacity. Hence the achievable specific energy, which is a product of the average redox voltage of the cell and the specific capacity in a Na-ion full-cell, is always lower than the stoichiometric O3 type NaxMO2 when typical P2/P3 NaxMO2 is used at the positive electrode.
Apart from the phase transitions during cycling, the low redox potential and moisture sensitivity of the material, which requires the storing and processing of these layered oxides in an inert atmosphere, are other major problems of the use of O3 NaxMO2 materials.
Komaba et al. in Inorg. Chem. 2012, 51, 6211-6220 (ref. 12) report acceptable results for a sodium layered oxide (NMO), that is Na1-xNi0.5Mn0.5O2, in the voltage range 2.2 to 3.8V but poor cyclability after charging to 4.5V. Likewise Kubota et al., in J. Phys. Chem. C 2015, 119, 166-175, reports a significant decrease in the discharge capacity for a NMO material when the charge is beyond a 3.8V plateau. This is shown to be in line with numerous reports (cf. p169) showing similar behaviours of these types of NMO materials having an O3 structure. Hence the cut-off voltage of these materials generally sets at around 4V.
Various modifications of the layered NaxMO2 material have been proposed in order to improve their electrochemical properties. In particular, it was proposed in the following documents to add Ni cations within the O3—NaNi0.5Mn0.5O2 (named hereafter NM) to partially replace Mn4+. Mariyappan et al. proposed in Adv. Energy Mater., 8, 1702599 (2018) (ref. 8), another partial Mn4+ substitution with Sn4+ within O3—NaNi0.5Mn0.5O2 in order to obtain NaNi0.5Mn0.5-xSnxO2, wherein x is a number between 0 and 0.5.
Zheng et al. proposed in Electrochimica Acta, 233, 284-291 (2017) (ref. 9), a partial Mn4+ substitution with Ti4+ to obtain Na0.9Ni0.45MnxTi0.55-xO2, wherein x is a number between 0 and 0.55.
WO 2014 009 710 A1 describes alkaline layered oxide compounds such as Na1.05Ni0.4Mn0.5Mg0.025Ti0.025O2 and Na1.05Ni0.4Ti0.025Mg0.025Mn0.5O2.
WO 2014 132 174 A1 describes alkaline layered oxide compounds such as Na1.05Ni0.40Mn0.50Mg0.025Ti0.025O2.
US 2015 020 713 8 A1 describes sodium layered oxide compounds such as NaNi0.50Mn0.25Ti0.25O2, NaNi0.5Mn0.225Ti0.225Zr0.05O2, and NaNi0.5Mn0.2Ti0.2Zr0.1O2.
US 2015 013 703 1 A1 describes processes to obtain an alkaline layered oxide compounds, such as NaNi0.4Mn0.4Cu0.1Ti0.1O2, NaNi0.45Mn0.45Cu0.05Ti0.05O2, NaNi0.45Mn0.45Mg0.05Ti0.05O2 in order to convert sodium ion materials into lithium ion materials using an ion exchange process.
US 2015/0194672 (Barker) discloses nickelate layered oxides which incorporate various other metals as dopants including zinc, calcium, magnesium, copper and cobalt. It does not disclose that compounds which comprise zinc can exhibit good performances at a voltage higher than 4.0 V, nor how to make such compounds.
US 2018/0269522 (Treacher) discloses using nickelate layered oxides which incorporate various other metals a dopants including zinc, calcium, magnesium, copper and cobalt as an active material of a positive electrode of a sodium ion cell. It recommends that the voltage to be applied does not exceed, or is less than, 4.3V for NaNi0.33Mn0.33Mg0.167Ti0.167O2.
None of the above documents discloses the partial substitution of Ni2+ by Zn2+ in order to obtain a more moisture stable component and/or a better, or at least equivalent, electrochemical performance than the one obtained with NVPF, especially at a voltage higher than 4.0 V, in particular higher than 4.3 V.
It is therefore an object of the invention to provide a new electroactive compound of the layered sodium oxide type, and electrochemical energy storage devices containing such compound, which would overcome one or several of these drawbacks of the materials and devices of the prior art and/or has one or more of the following properties:
It has now been found that introducing Zn2+ in an O3-type NaNi0.5Mn0.5O2 (NM) layered oxide provides, in particular in presence of titanium, a compound that is unexpectedly provided with at least one, and preferably more of the above-mentioned properties.
Therefore one object of the invention is a compound of formula NaxNi0.5-yZnyMn0.5-zTizO2 (hereafter named ZNMT), wherein x is a number ranging from 0.7 to 1.1, y is greater than 0 and less or equal to 0.1, and z is a number between 0 to 0.5 (greater than 0 and less than 0.5). x may range from 0.8 to 1.1. and, preferably, x is about 1 or equal to 1. Such a compound is electrochemically active. According to a particular embodiment of the invention the compound is a homogeneous compound or material.
The active compound is preferably a compound of formula NaxNi0.5-yZnyMn0.5-zTizO2, wherein x is about 1, y is a number ranging from 0.01 to 0.1, and z is a number ranging from 0.01 to 0.45. The active compound is also preferably a compound of formula NaxNi0.5-yZnyMn0.5-zTizO2, wherein x is about 1, y is a number ranging from 0.03 to 0.1, and z is a number ranging from 0.05 to 0.25. It is further preferred that the active compound is of formula NaxNi0.5-yZnyMn0.5-zTizO2, wherein x is about 1, y is a number ranging from 0.04 to 0.1, and z is a number ranging from 0.08 to 0.22.
The following compounds are also preferred: NaNi0.45Zn0.05Mn0.4Ti0.1O2 (named hereafter as ZNMT1), NaNi0.4Zn0.1Mn0.4Ti0.1O2 (named hereafter as ZNMT2) and NaNi0.45Zn0.05Mn0.3Ti0.2O2 (named hereafter as ZNMT3) and their derivatives. By derivative it is meant that each the atomic percentage of each element can vary from ±10%.
According to a variant of the invention the active compound have the general formula (V) NaxNiy-zZnzMn(1-y-z)TinO2, wherein x is a number ranging from above 0.7 to 1.1, y is greater than 0 and less or equal to 0.5, z is a number between 0 to 0.1 (greater than 0 and less than 0.5) and n is a number between 0 to 0.6. x may range from 0.8 to 1.1. and, preferably, x is about 1 or equal to 1. Such a compound is electrochemically active.
The compound having the general formula NaxNi0.45Zn0.05Mn0.35Ti0.15O2 (IV) wherein x ranges from 1.1 to less than 0.7, preferably from 1 to 0.8, is also a compound according to the invention.
According to a particular embodiment of the invention a compound having the formula NaNi0.4Zn0.1Mn0.4Ti0.1O2 may be excluded from the scope of the invention.
According to a particular embodiment of the invention a compound having the formula NaNi0.4Zn0.0.5Mn0.45Ti0.05O2 may be excluded from the scope of the invention.
According to a particular embodiment of the invention a compound having the general formula NaNi0.5-xTi0.5-x′Znx′Mnx′O2, where in x′ ranges from 0 to less 0.5, may be excluded from the scope of the invention.
According to a particular embodiment of the invention a compound having the general formula NaNi0.5-x′Tiy′Znx′Mn0.5-y′O2 , wherein x′ ranges from 0 to less 0.5 and y′ ranges from 0 to less 0.5, may be excluded from the scope of the invention. According to a particular embodiment of the invention a compound having the general formula NaNi0.5-x′Ti0.25+x′/2Znx′Mn0.25-x′/2O2, wherein x′ ranges from 0 to less 0.5, may be excluded from the scope of the invention.
The sodium layered oxide compound of the invention can advantageously be in a powdered form. Preferably, the layered oxide powder can be prepared with ball milling, preferably with powder to ball weight ratio of 1:20.
Another object of the invention is a conductive material which comprises the layered oxide compound (or active compound) and an electronically conductive additive. The electronically conductive additive may comprise, essentially consist or consist of carbon black (i.e. entirely disordered or substantially disordered carbon, CAS:1333-86-4) such as super-P™, C-45™, C-65™, acetylene black, Ketjen Black™ volcano carbon etc., usually in a powder form. Substantially disordered carbon containing a small proportion of graphitized carbon is preferred. This conductive material can be prepared using ball milling of the layered oxide powder and of the other conductive material can be prepared with ball milling, preferably with powder to ball weight ratio of 1:35. The material can be used in particular to manufacture positive electrode, (i.e. as a positive electrode material).
The concentration of the electronically conductive additive preferably ranges from 10 to 20 w/w % in respect of the total weight of the layered oxide compound(s) and of the conductive additive. Preferably the concentration is about 15 w/w %.
According to a particular embodiment, no polymer binder is present, more preferably no binding materials are used. The conductive material can be in the shape of a powder, which can be compressed into shape (e.g. a disc) or not.
Alternatively, the conductive material can further comprise a binder material which allows its casting into shape. This binder can be a polymer binder. The polymer binder can advantageously comprise, consist or essentially consist of polyvinylidene fluoride and/or its derivatives. The binder material can be admixed with a suitable solvent, which is advantageously non-aqueous (e.g. organic) such as N-methyl pyrrolidine (NMP), before it is cast onto a support.
In one embodiment, the compound of the invention has, or allows, an initial discharge specific capacity of at least 120 mAh·g−1, preferably of at least about 150 mAh·g−1, and advantageously 220 mAh·g−1, as measured at a discharge rate which may range from C/30 to 1C, in particular which may be a discharge rate of about C/10. A C/10 rate corresponds to a total removal from, or insertion to, sodium ions from the compounds of the invention in 10 hours. For example, the initial discharge capacity of the cell may range from 140 mAh·g−1 to 250 mAh·g−1.
In another embodiment, the compound of the invention has, or allows, a specific energy (Wh√kg−1) which is a product from specific capacity expressed in Ah√kg−1 and average redox potential of the cell, expressed in volts. The specific energy can be normalized for the total mass of electrode material on both positive and negative electrodes in the cell.
In another embodiment of the compound of the invention the specific energy of the cell is at least about 200 Wh·kg−1 when cycled at a voltage inferior to 4 V and/or the specific energy is at least about 250 Wh·kg−1 when cycled at a voltage superior to 4 V. For example, the specific energy may range from 200 Wh·kg−1 to 300 Wh·kg−1, preferably from 240 Wh·kg−1 to 270 Wh·kg−1.
The capacity retention (or charge retention) can be defined as the fraction of the initial discharge specific capacity available under specific conditions of discharge. The energy retention can be defined as the fraction of the initial specific energy available under specific conditions of discharge. By initial capacity/Initial energy it is meant that the specific capacity/energy obtained at the end of the first complete cycle (i.e. of a cell) at a discharged state (i.e. sodiated state).
In another preferred embodiment, the compound of the invention has, or allows, an energy retention superior to 70% over a hundred cycles when cycled at a voltage superior to 4 V. In particular the voltage may be chosen between 4 and 5 V, preferably at, or above, 4.4 V. The percentage energy retention of the compound of the invention may range from 73% to 99%; preferably from 78% to 95%, e.g. from 80 to 90%.
According to another embodiment the energy retention of the material or the cell is superior to 80% over a hundred cycles when cycled at a voltage up, or above to 4 V, (e.g. 4.4 V), preferably the energy retention is over or around 90%.
According to another aspect, the invention features an electrochemical cell which comprises:
In one preferred embodiment, the positive electrode comprises, consists, or consists essentially of the conductive material of the invention as described above which is then used as a positive electrode material. The electronically conductive material additive is advantageously carbon black.
In one embodiment, the negative electrode has an active material which comprises, consists or essentially consists of sodium metal. This is particularly the case when the electrochemical cell is in half-cell configuration.
In another embodiment, which is actually preferred, the negative electrode has an active material which can comprise, consist essentially of, or consist of hard carbon, antimony, tin, phosphorus and a combination thereof. Such a material is particularly adapted to a full-cell configuration.
In a preferred embodiment, the negative electrode comprises a carbonaceous compound, preferably a hard carbon powder as an active material. Raman spectra of hard carbon exhibit two characteristic bands at ca. 1350 (D-band) and 1580 (G-band) cm−1 corresponding respectively to the E2g graphitic mode and the defect-induced mode. The hard carbon powder may have particles sized of 1-20 μm and a specific surface of 1-10 m2·g−1. The active material can be mixed with an electronically conductive additive such as carbon black to obtain a material for the negative electrode. The concentration of electronically conductive material may range from 1 to 8 w/w %, for example 4 w/w %, in respect of the total weight of the active material and the additive.
Such a negative electrode material can further comprise a binder material which allows its casting into shape, and/or have cohesive, conductive or dispersive properties. This binder can be a polymer binder. The polymer binder can advantageously comprise, essentially consist, or consist of carboxymethyl cellulose sodium, and/or its derivative. It can also comprise, consist or essentially consists of polyvinylidene fluoride and/or its derivatives. The binder material can be admixed with a suitable solvent such as N-methyl pyrrolidine (NMP) and/or water before it is cast onto a support.
When an active material, an electronically conductive material and a binder is used their respective proportions in weight may be for example 92:4:4.
The current collector for either or both of the electrodes can be made of any suitable material such as, for example, stainless-steel, aluminum, copper or nickel.
The electrolyte comprises a suitable salt which may advantageously be selected in the group consisting of sodium hexafluorophosphate (NaPF6), sodium perchlorate (NaClO4), sodium bis (fluorosulfonyl) imide (NaFSI), sodium bis(trifluoromethanesulfonyl)imide (NaTFSI), sodium bis(pentafluoroethanesulfonyl)imide (NaBETI), sodium tetrafluoroborate (NaBF4) and a mixture thereof. The electrolyte further comprises a non-aqueous solvent, for example selected from the group consisting of dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), diethyl carbonate (DEC), propylene carbonate (PC), ethylene carbonate (EC), ethyl acetate (EA), ethyl propionate (EP), methyl propionate (MP), bis(2-methoxyethyl) ether (Diglyme) and a mixture thereof. The proportion of said solvent may range from 60 w/w % to 98 w/w % in the total weight of the electrolyte
The concentration of the salt in said solvent may range from 0.1 mol·L−1 to 3 mol·L−1, advantageously from 0.5 mol·L−1 to 2 mol·L−1.
According to a preferred aspect of the invention, an electrolyte additive can be added to the electrolyte. Such an electrolyte additive can help to improve the high temperature performance and low self-discharge performance of Na ion cell or battery of the invention. The additive can be selected from the group consisting of vinylene carbonate (VC), 1,3-Propanesultone (PS), Succinonitrile (SN), Sodium difluoro(oxalato)borate (NaODFB) and a mixture thereof. The concentration of vinylene carbonate (VC) may range from 0.1 to 10 w/w %, advantageously from 0.5 to 5.0 w/w %, in respect of the total weight of the electrolyte. The concentration of 1,3-Propanesultone (PS) may range from 0.1 to 5 w/w %, preferably from 0.5 to 3.0 w/w %, in respect of the total weight of the electrolyte. The concentration of Succinonitrile (SN) may range from 0.1 to 5 w/w %, preferably from 0.5 to 2.0 w/w %, in respect of the total weight of the electrolyte. The concentration of Sodium difluoro(oxalato)borate (NaODFB) may range from 0.05 to 10 w/w %, preferably from 0.2 to 1.0 w/w %, in respect of the total weight of the electrolyte.
The separator is a permeable membrane or film, preferably microporous. The separator may be made of a material which can be selected from the group consisting of glass fiber, polyolefin separators (including polypropylene (PP) and polyethylene (PE), cellulose and a combination thereof. The separator may be an arrangement of several layers of material, in particular of PP and/or PE.
Yet another aspect of the invention is a battery which comprises one or more electrochemical cell according to the invention and may further include external connections. These connections can advantageously be adapted to connect to and power, electrical devices. The configuration of such a battery can be for example, a coin cell, a pouch cell, a cylindrical (of various dimensions, such as: 18650, 21700, 36500 etc.) cell, or a prismatic cell.
The sodium layered oxide active compound according to the invention can be prepared by solid state synthesis according to generally known principle. In a nutshell, precursors which are oxides such as Na2CO3, NiO, ZnO, Mn2O3, and TiO2, are ground or milled together according to required proportions for example, using ball milling. The mixture is then heated at a temperature superior to 800° C., preferably superior or equal to 900° C., under an inert and/or air atmosphere. This is a first annealing, or calcination, step. A process to make these compounds falls within the scope of the invention. Hence a compound obtained or obtainable according to the process of the invention is also an object of the invention.
Advantageously this process according to the invention comprises a second calcination step at around 1000° C. which is advantageously carried out after a cooling step. Such a process was found to produce homogenous material with a phase which is single or approaching single phase and does little to none multiple phases. The expression “around 1000° C.” encompasses a temperature ranging from 950° C. to 1100° C., preferably from 980° C. to 1020° C.). This second calcination step can be carried out for a period ranging from 1 h to 24 h, preferably for a period ranging from 8 h to 16 h, and more preferably for a period ranging from 10 h to 13 h. A period of about 12 hours was found particularly advantageous. As for the first calcination step, the second calcination step can be carried out under an inert and/or air atmosphere. Air atmosphere is preferred. The second calcination step, or both the first and the second calcination steps can be carried out at a heating rate ranging from 1 to 10° C. per minutes, and is preferably of 3° C. per minute.
It is also advantageous that when cooling step is carried out, the compound be cooled at a predetermined rated, which may range from 1 to 5° C. per minute, and is preferably of 1° C. per minute. Such a rate can be important to obtain best results.
A particularly advantageous step is to carry out a step of grinding of the, preferably cooled, compound obtained after the first calcination, or annealing, step. This grinding can be carried out using known method, such as mortar and pestle or ball milling. The powder to ball ratio can be around 1:10 to around 1:20, but is preferably 1:10.
It was found that a combination of a second calcination step at around 1000° C., preferably around 12 hours, with an intermediary grinding step, provides a particularly homogenous material (compound). Furthermore, it was further found that repeating this second calcination step a third time, together with a further intermediate grinding step, was advantageous in term of homogeneity.
According to a particular embodiment of the process of the invention there is no pelletizing step before the second, and preferably any, calcination step(s).
Likewise, the use of the compound, the conductive material, the cell or the battery of the invention in an electrochemical device is also part of the invention as well as an electrode comprising the compound of the invention and a support such as the ones above described.
The use of the battery according to the invention includes for example its incorporation in microgrids stabilizing power grids, electrochemical storage devices for intermittent renewable energy (e.g. solar, wind energy), mobile storage devices for electric vehicles (end-of-life rechargeable buses, rental vehicle fleets), domestic electrical power storage devices, emergency power-supply or energy storage device for hospitals, schools, factories, computer clusters, servers, companies, and any other public and/or private buildings or infrastructure. The compound according to the invention or a device incorporating said compound can be of use for example for industries in following fields: automobile, computer, banking, video game, leisure, creative, cultural, cosmetic, life science, aviation, pharmaceutical, metal and steel, rail, military, nuclear, naval, space, food, agriculture, construction, glass, cement, textile, packaging, electronics, petrochemical, and chemical industries.
Some technical effects associated with the compounds according to the invention are summarized as follows.
The foregoing and other objects, aspects, features and advantages of the invention will become more apparent from the following examples and from the claims.
The present invention will now be described with reference to the following figures in which:
Three compounds according to the present invention were prepared by solid state synthesis. All the precursors used in the synthesis were purchased from Sigma Aldrich with nearly 99 w/w % or above purity. The exact weight of each precursor oxides used to prepare about 1 g of the final sodium transition metal layered oxide compounds according to the invention, named ZNMT 1, 2 and 3, is shown below in Table 1.
The weight of each compound was calculated as per the stoichiometric ratio and no extra sodium was used in the synthesis in order to compensate the sodium loss which may occur while calcining at high temperature, i.e. above 800° C. For the purpose of synthesizing all the above layered oxides, the same following method was used: The powdered precursor oxides were individually weighed each according to the required stoichiometry and then mixed together. The powders were ground with a mortar and pestle for 15 minutes followed by a ball milling step for 1 hour. The ball milling step was carried out using a SPEX 8000M™ mixer mill using ball milling balls and containers made of hardened steel. Ball to powder ratio of 1:20 was used for milling the precursors. The milled precursors were collected from the ball milling vial and transferred to alumina crucibles.
During a first annealing step, the precursors were calcined at 900° C. for 12 h in air atmosphere with a heating rate of 3° C. min−1 followed by a slow cooling to 300° C. with the cooling rate of 1° C. min−1. Hence, the total reaction period was nearly 27 hours for the first calcination step (about 5 h for heating, 12 hours of dwell period at constant temperature 900° C., and about 10 hours of cooling).
The sodium transition metal layered oxide product thus removed from the furnace at 300° C. After cooling it until ambient temperature in air atmosphere, the oxide product was grinded (in air atmosphere) for 15 minutes with a mortar and pestle to ensure homogeneity of the material.
The product from the first annealing step was treated for a second annealing (or calcination) step at 1000° C. for 12 h in air. Heating and cooling rates were maintained at 3° C. min−1 and 1° C. min−1, respectively, as explained above. The oxide materials after the second calcination step were removed from the furnace when the temperature had reached 300° C. and transferred immediately (within 10 minutes) to an argon filled glove box with the minimal exposure to atmospheric air, especially to moisture. The materials obtained after the second calcination step showed some NiO impurities (nearly 5 w/w %), as shown in XRD patterns in
In order to demonstrate the advantageous characteristics and properties of the compounds of the invention, these were compared to other sodium transition metal O3 layered oxide oxides not part of the invention. They were prepared according to the same method which is described in Example 1a. Again, the exact weight of each precursor used to prepare about 1 g of these comparative oxides is shown below in Table 2.
The phase purity and structure of the materials were analyzed by powder X-ray diffraction (XRD) analysis. X-ray diffractive measurement such as X-ray diffraction (XRD) is carried out to determine the crystalline structure of synthesized compounds and/or materials. XRD can be carried out operando, in order to monitor crystalline structure of the compounds and/or of the materials during a realistic cycling condition, using a specific cell designed for this purpose. As a result, no demounting of the cell is necessary and thus the environment in which the active compounds are located is preserved during the non-destructive measurement, such as XRD. In addition, this type of analysis can be particularly useful for alkali-ion technology which requires a well-controlled humidity and a sealed environment.
The XRD patterns were collected using Bruker d8 advanced diffractometer. The following parameters were set to collect X-ray pattern data:
The data thus obtained were analyzed by Fullprof software, a crystallographic tool developed by the Institut Laue-Langevin for Rietveld profiling matching. The XRD patterns were compared to the integrated database of the software and were refined when required.
The stability of the materials on exposure to moist air was analyzed by storing the material at 55% RH (relative humidity) for 24 hours and analyzing the XRD evolution before and after the storage. The controlled humidity of 55% RH was maintained using a saturated solution of Mg (NO3)2.6H2O (Sigma Aldrich) in water. The saturated magnesium nitrate solution and samples under analysis were kept in a sealed desiccator to ensure the required relative humidity.
The XRD patterns of the resultant oxide powders were obtained using powder XRD analysis. The XRD pattern exhibited a single-phase material.
The materials obtained after the second calcination step showed some (nearly 5 w/w %) NiO impurities, as shown in XRD patterns in
Transmission electron microscopy (TEM) enables a high resolution (up to sub-angstrom range) imaging. When associated with energy dispersive X-ray spectroscopy (EDS) mapping, the TEM allows to determine the crystal structure of a much localized zone of the specimen.
The High-resolution transmission electron microscopy (HRTEM) with energy dispersive X-ray spectroscopy (EDS) mapping was carried out to check the homogeneity of the as prepared (pristine) materials. FEI Titan3 microscope (ThermoFisher Scientific) operated at 200-300 kV was used for these analyses.
The specimens for the TEM analysis were prepared in the argon filled glove box. The dry pristine material was pressed to the copper grid, which was covered with holey carbon films. Then the grid was slightly tapped in order to remove the loose powders. The copper grid with the sodium layered oxide particles for analysis was then carefully transferred to the TEM chamber without exposing to atmospheric air using a Gatan (inc.) vacuum transfer holder.
The TEM-EDS mapping at different positions of the particle obtained after the first calcination step showed sodium rich and sodium poor phases. However, the material obtained after the second calcination step at 1000° C. for 12 h were homogeneous.
The layered oxides prepared were used for their electrochemical performances and tested in half-cells and full-cells configuration.
The electrodes according to the invention were made by selecting one or more layered oxide compound obtained in Examples 1a.
The layered oxide active materials (positive or working electrode) in all cell configurations were used in powdered form. The layered oxide materials for electrochemical analyses were mixed with 15 w/w % carbon black (super P carbon, TIMCAL) and ball milled for 30 min using SPEX 8000M mixer mill. Hardened steel ball milling container with balls made of hardened steel was used to mill 3 g of oxide with a compound to ball weight ratio of 1:35.
In the example, the electrodes were prepared without binder but use of a binder is encompassed by the invention in particular for commercial products. It should be noted that the use of the powder without binder has shown the results that were equivalent to those prepared with binder (e.g. PVDF and NMP as solvent). Indeed, the preparation without the binder can be of interest in terms of proper loading of each component and of convenience to implement. The current collector used was a thin sheet of aluminum foil.
Electrodes put together in order to achieve Operando XRD measurements require a special caution while preparing the electrode according to the invention. In reference to the
The operando XRD measurements were carried out in home-made Swagelok type cells made of stainless-steel body (bore) 12 and a stainless-steel plunger 2 on one side and a Be window 16 in the other side as current collectors. The way these cells were assembled is further described in Example 6.
Hard carbon film was used as a negative electrode material for full-cell configuration and it was prepared at ambient atmosphere outside the glovebox. The hard carbon negative electrode powder was provided by Aekyung Petrochemical, Republic of Korea. The average particle size and the BET surface area of this hard carbon was 9 μm and 3.29 m2·g−1 respectively. The hard carbon powder thus obtained was mixed with 4 w/w % conducting carbon (super P carbon from TIMCAL) and binder. The binder used here were either PVDF in N-methyl pyrrolidine (NMP) or carboxymethyl cellulose sodium and/or its derivatives in water solvent. The negative electrode slurry was prepared by mixing active material, conducting carbon and binder in NMP respectively in the ratio of 92:4:4. The slurry thus obtained was coated on an Al foil with a mass loading of 5-6 mg·cm−2. The coated hard carbon films were calendared to reduce the porosity of the electrode to nearly 50%. The electrodes were cut into circular discs of 8-10 mm diameter and were dried at 80° C. before using in the full-cell assembly and stored in the argon filled glove box.
Two types of cells were used in half-cell configuration:
All cells (i.e. half-cell and full-cells (see below)) were assembled in Argon filled glove box (MBRAUN, Germany) and the cells were ensured to be air tight. The glove box atmosphere during the assembly of the cells was maintained at <0.1 ppm of O2 and <0.1 ppm of H2O.
For both cells, the positive powder electrode was covered completely with 3 layers of glass fiber separator made of fine fiber glass and purchased from Whatmann, model GF/D (Pore Size: 2.7 μm, Diameter: 5.5 cm; Thickness: 675 μm). In addition, 1M solution of NaPF6 in propylene carbonate solvent was used as electrolyte for all cell assemblies.
The configuration of both cells is explained below.
With reference to
The sodium layered oxide active material 4 mixed with 15 w/w % carbon was weighed (4-10 mg) and placed in the middle of the aluminum plunger 2 (diameter=10 mm), and used as the positive electrode. The negative electrode part used stainless steel disc 5 of 1 mm thickness and 9-10 mm diameter as current collector. A stainless-steel spring 6 and a stainless-steel plunger 2 were covered on top of the stainless-steel disc 5 to apply pressure and the cell 1 was closed both sides with the bulkhead unions (SS-810-6) using nylon ferrules (not represented).
The separator 7 was cut into circular disc of diameter of about 11 mm for electrochemical test cells 1. Around 0.8-1 mL of the electrolyte was used to wet three layers of the separator 7.
The sodium metal 8 for the counter (negative) electrode was cut into a small piece and pressed onto a stainless-steel disc 5 of about 1 mm thickness, using a plastic tweezer. The diameter of the stainless-steel disc 5 was about 8 mm for Swagelok half-cells 1. The stainless-steel disc 5 with the sodium metal 8 was placed on the top of the separator 7 in such a way that the sodium metal 8 is in contact with the separator 7. The cell 1 was finally closed using a screw top, by placing a stainless-steel spring 6 and a stainless-steel plunger 2 on the negative electrode side. The screw top and the main cell body were separated by nylon ferrules purchased from Swagelok company.
With reference to
The Be window 16 was covered with an aluminum foil (purchased from Goodfellow, France) of thickness 4-5 μm to protect the Be window 16 from the reaction with electrolyte at high potentials (above 4 V vs Na+/Na). Once the Be window 16 and aluminum foil (not represented) were placed in the outer ring 14, the ring 14 was connected with the main body 12 through an O-ring and the assembly of the ring 14 and the main body 12 were screwed to be held together. A stainless-steel disc 5 of 1 mm thickness and 1.5 cm diameter was used as current collector in the negative electrode side. A stainless-steel spring 6 and stainless-steel plunger 2′ of 2 cm diameter was used in the negative side to apply pressure to the cell 10 and the negative part was closed with stainless steel union and nylon ferrules (not represented).
The separator 7 was cut into circular disc of diameter of about 20 mm for the operando XRD cells 10. About 2 mL of the electrolyte was used to wet 3 layers of the separators 7.
The sodium metal for the counter electrode was cut into a small piece and pressed onto a stainless-steel disc 5 (about 1 mm thickness) using a plastic tweezer. The diameter of the stainless-steel disc 5 was about 15 mm for the operando XRD cell.
The cell 10 was finally closed using a screw top, by placing a stainless-steel spring 6 and a stainless-steel plunger 2′ on the negative electrode side. The screw top and the main cell body 12 were separated by nylon ferrules (not shown) purchased from Swagelok company.
All the cell assemblies were done in argon filled glove box (O2 level <0.1 ppm and H2O level <0.1 ppm), however the testing of the cells was carried out in air atmosphere as the assembled cells were ensured to be air tight.
The cells once assembled were taken out of the glove box and tested for their electrochemical performance. The positive electrode side and the steel plunger on the negative electrode side were used to connect the cell to the potentiostat for analyzing the electrochemical performances.
The Swagelok half-cells thus assembled were cycled galvanostatically (at a constant current) at C/10 within the voltage window of 1.5-4V vs. Na+/Na and 1.5-4.5 V vs. Na+/Na. The 1C rate (where 1 C=246.7 mAh·g−1) for the measurements was calculated using the following formula:
C-rate (mAh)=Weight of the active compound used in cell assembly (in g)×26.8 (mAh·mol−1)/Molecular weight of the active compound (g·mol−1).
Galvanostatic cycling is an electrochemical measurement which consists of observing the voltage evolution of an electrochemical cell at a given current. A stagnation or variation of potential can be associated with an onset of an electrochemical phenomenon. Galvanostatic cycling was carried out for each type of cell (i.e. half-cell or full cell) tested.
Since all the studied sodium layered oxides were prepared to have one sodium at the end of the synthesis, the capacity (mAh·g−1) was computed assuming a complete removal of sodium from the structure. Approximately 4-10 mg of the active material was used for Swagelok half-cells and around 40 mg of the active material was used in operando XRD cells. The electrochemical analyses were carried out in Biologic (Seyssinet-Pariset, France) potentiostat/galvanostat model MPG-2 or VMP-3.
The cell 10 for operando XRD measurement was placed on the XRD holder using a home-made Teflon holder 18 and connected with a potentiostat VSP 50 (Biologic) for electrochemical analysis (
With reference to
The positive to negative material weight ratio were balanced by harmonizing the practical capacity of each electrode active compound used (i.e. ZNMT/Hard carbon). For example, the hard carbon electrode 22 used in all cell assemblies exhibits a first cycle discharge capacity of 300 mAh·g−1. In this case, as the positive electrode shows about 180 mAh·g−1, the positive to negative material weight ratio of (ZNMT)/(Hard carbon) about 1.7:1 was used in order to counterbalance the capacity of positive electrode. However, the negative hard carbon electrode 22 was used in about 4 w/w % excess to avoid any sodium plating. In other words, an additional amount of negative electrode active material in mg is used to get an additional capacity of 4% to the actual amount of negative hard carbon required to balance the positive electrode, i.e. the weight in mg of active material corresponding to 12 mAh·g−1, as the hard carbon shows 300 mAh·g−1 practical specific charge capacity.
In other words, once the electrode capacity was known, the quantity of active material on either electrode was adjusted so that, if the capacity ratio of each electrodes is expressed as follows:
Capacity ratio=Positive cell capacity/Negative cell capacity=pc/nc
Then, the total mass of active compound of each electrode was adjusted so that the negative electrode mass of active compound is as follows:
Negative electrode mass=positive electrode mass×(pc/nc), where pc is lower than nc.
The positive electrodes in all the full cells 20 were used in the powder form 24 after mixing with 15 w/w % carbon. The 2032-coin cell components were purchased from Shenzhen Yongxingyue precision machinery co. ltd (China) and were made of stainless steel. The positive electrode case 26 of the 2032 cell was covered with an aluminum foil 28 as the oxidation potential used for the cycling was above 4 V vs. Na+/Na that can leads to oxidation of stainless-steel components. The sodium layered oxide active material 24 mixed with 15 w/w % carbon was weighed and placed in the middle of the positive electrode case with aluminum (Al) foil. Two layers of separators 7′ with the diameter of 18-19 mm were kept on the top of the positive electrode powder 24 by taking care not to spread the powder to other parts of the cell 20. 0.7 mL of electrolyte was used to wet the separator 7′ on top of which hard carbon film 22 used as the negative electrode was placed. The carbon film 22 was covered then by a stainless-steel disc 5′ on top of which the spring 6′ was placed to provide pressure to the electrodes. Finally, the coin cell 20 was closed by the negative electrode compartment 30 having an O-ring and crimped using the coin cell crimping machine bought from MTI Corporation.
The assembled coin cells 30 were tested in Biologic battery cycler BCS-8 at C/10 within the voltage window of 1.2-4 or 4.4 V. A lower discharge potential of 1 V is used exclusively for NaNi0.5Mn0.5O2 (NM) due to its low redox process. All electrochemical analyses were carried out at room temperature.
The electrodes, half-cells, and/or full cells used for comparative purposes were made, assembled and characterized using the same methods described above in examples 1 to 7, unless specific conditions are explicitly mentioned.
On the other hand, the XRD patterns of ZNMT1 remain stable and no additional peaks appear despite 24 h of exposure to humidity. Therefore, ZNMT1 shows an improved stability on exposure to moist air.
The same stability is shown by ZNMT2 and ZNMT3 on
The term “doping” according to the Electrochemical dictionary, Allen Bard, Springer Verlag, is “. . . a controlled addition of a relatively small amount of foreign component (dopant) to solid materials in order to change their properties, or the process of adding impurity atoms. As a rule, dopant ions or atoms are incorporated into the crystal lattice of host materials. Depending on the type of host lattice and dopant, the incorporation of foreign species may lead to creation of electronic defects, other point defects, and defect clusters.” However, the term “doping” is used hereafter, by extension, to relate to the presence of some elements in a compound which are in relatively smaller amounts than the other elements.
Electrochemical characterizations were carried out for the half-cells (Na metal negative electrode) and the full cells (Hard carbon negative electrode) as described above. The positive electrode was made of the material of the invention ZNMT1 and compared to similar cells made of other layered oxides: ZNM, NMT and NM.
The results are shown in
Each peak of the differential capacity curve corresponds to a plateau in the voltage-capacity curve. In particular, in 3-4 V vs. Na+/Na voltage range, those peaks reveal the above-mentioned O3 type layered oxide phase transitions.
When comparing NM and ZNM or NM and NMT, the individual doping with Zn2+ or with Ti4+ reduces the associated O3 phase transitions. Specifically, the ZNMT1 shows the best reduction of phase transitions compared to comparative examples.
The right-side plots of
Among the all studied materials, Zn2+, Ti4+ co-doped material ZNMT1 shows the best stability of the initial discharge capacity over cycles. In other words, the best capacity retention is observed with ZNMT1.
In this example the role of Mn4+ within the sodium O3-layered oxide is illustrated. In order to understand the role of Mn4+ in the doped NaNi0.5Mn0.5O2 (NM) materials, the powder XRD patterns (
The XRD pattern in
The synthesis of the O3 phase is possible with increasing Ti4+ substitution for Mn4+ in the NM. Indeed, it is possible to obtain phase pure material even with the complete replacement of Mn4+ by Ti4+ to produce NZT. However, it was found that the presence of Mn4+ is essential to have balanced ionic and covalent characters of the metal-oxygen bonds.
In this example, Mg2+ (ionic radius=0.76 Å) having a similar ionic radius as that of Zn2+ (ionic radius=0.74 Å) was used to replace Zn2+.
The phase transition from O3 to P3 is observed with all compounds irrespective of the Ti4+ and Zn2+ doping. It shows that the stabilization due to Na-vacancy ordering in the P3 structure is higher than the destabilization created due to Zn2+ (steric effect) and the increase in ionicity of the crystal lattice. In contrast, a notable difference is observed with 4 V O-type phase, whose evolution is delayed with Ti4+ substitution and completely eliminated with Zn2+, Ti4+ co-doped ZNMT1 material within the studied voltage window.
The electrochemical analyses were done in operando XRD half-cells using metallic sodium as negative electrode and the cells were cycled at C/10 rate.
On the one hand, the potential according to the amount of sodium curve in the left shows that both NM and NMT materials reveal a plateau at the end of charge, a signature of presence of two separate phases (O1 and O3), in which the O1 phase has a very small sized unit cell,—the smallest repeating unit having the full symmetry of the crystal structure—in comparison with the pristine material.
The extent of change in unit cell can be directly visualized from the d-value of the (003) peak, which is an indicator of the c-axis of the unit cell. If the peak appears at high angle, the corresponding d-spacing is small and hence the unit cell is small. For the NM materials, the d-spacing varies from 5.21 Å for the pristine O3 to 4.36 Å for the fully charged phase. Similarly, a reduction in d-spacing of 5.29 Å to 4.41 Å was observed with NMT phase on moving from pristine O3 to charged O-type phase. These reductions observed with NM and NMT represents the concomitant reduction in the unit cell volume.
On the other hand, ZNMT shows no plateau at the end of the charge. Furthermore, XRD features at a charged state is characterized by a broad peak with (003) at 5.17 Å which shows a very small reduction from the pristine d (003)=5.25 Å. The results indicate that the overall change in the unit cell of ZNMT is very low in comparison to the NMT and NM materials. The observation of broad peaks in the XRD represents a hybrid structure with different layer stacking and/or stacking faults. The behavior is expected to be associated with the partial retention of P3 stacking at the end of charge and/or the migration of transition metal ion to the van der Waals gap that reduce further gliding of layer to form O-type phase with reduced unit cell volume.
Due to such reduced phase transitions and small change in unit cell volume, the ZNMT1 retains its structural stability on long cycling, thereby improving the cycle life of the material even in the extended voltage window of 1.2-4.4 V (see
The energy evolution for these samples is similar and the difference between each specimen may go within the error limit.
In addition, a full cell using the polyanionic material Na3V2(PO4)2F3 (named as NVPF) received from Energy hub, Amiens, was also tested for comparative purposes. The data obtained for NVPF are identical for
The energies for all the specimen were normalized for the total mass of positive and negative active materials on the electrodes. Best retention in energy is observed for ZNMT1 (about 10% of decrease after a hundred cycles) which is in accordance with the reduced phase transitions observed in Example 14, whereas NVPF shows almost 25% of decrease after a hundred cycles, despite a superior discharge energy at pristine state (i.e. after the first cycle) (300 Wh·kg−1 for NVPF against 225 Wh·kg−1 for ZNMT1)
Best retention in energy is observed for ZNMT1 (20% of decrease after a hundred cycles), which is in accordance with the reduced phase transitions observed in Examples 9 and 15.
The results obtained at a voltage of 4.4 V, a condition that had not been favorable to sodium O3-layered oxide material to date, confirm a superior performance of ZNMT1 compared to NVPF, as the latter was being characterized in an optimized condition to maximize its performance.
ZNMT1 can be cycled to a voltage higher than 4.0 V without a significant loss over a hundred cycles. For example, 90% of initial capacity is preserved over a hundred cycles at 4.0 V and 80% of initial capacity is preserved over a hundred cycles at 4.4 V given that NVPF shows a steeper decrease of capacity (about 75% of initial capacity is preserved at 4.4 V). Zn2+ enhances the steric effect, which effectively reduces the phase transitions during cycling.
In this example, the amount of sodium (x) in the pristine phase is varied from 0.7 to 1. Compounds ZNMT1 (1 Na), ZNMT1.1 (0.9 Na), ZNMT1.2 (0.8 Na) and ZNMT 1.3 (0.7 Na) of the general formula NaxNi0.45Zn0.05Mn0.4Ti0.1O2 were analysed.
Likewise the galvanostatic charge-discharge cycle of ZNMT1 (1 Na), ZNMT1.1 (0.9 Na), ZNMT1.2 (0.8 Na) and ZNMT 1.3 (0.7 Na) of
Another compound according to the invention was synthesised. This compound have the formula NaNi0.45Zn0.05Mn0.35Ti0.15O2 (IV) was synthesised according to the method above described and tested. Its characteristics are shown in
The compounds of the invention made according to the process of the invention exhibit better homogeneity and hence better capacity (energy retention) than compounds of the invention made according to standard methods.
To demonstrate the superiority of the compound obtained according to the process of the invention, comparative data were obtained. A ZNMT1-900 compound was synthesized using a temperature of 900° C./12 h in the second annealing step instead of one of 1000° C./12 h. Furthermore no intermediate grinding was carried out between two annealing steps. The compound thus produced, ZNMT1-900, was compared to the compound ZNMT1 (renamed ZNMT1-1000/12 h to better distinguish the two ZNMT1 compounds) and ZNMT1-1000/24 h (see
This compound ZNMT1-1000/24 h was obtained by carrying out the process of ZNMT1 (aka ZNMT1-1000/12 h), but adding an additional (third) annealing step at 1000° C. for 12 hours, after an additional intermediate cooling/grinding step.
With reference to
It was also noted that ZNMT2 (NaNi0.4Zn0.1Mn0.4Ti0.1O2) could not be satisfactorily synthesised when both annealing were carried out at 900° C., for either 12 or 24 h. The resulting compounds had ZnO impurities which made the material not acceptable for a use in full-cells because the phase was not pure enough. Only when the temperature of the second annealing step was increased to 1000° C., the ZnO impurities disappeared. This is clearly shown in
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| Number | Date | Country | Kind |
|---|---|---|---|
| 19305827.8 | Jun 2019 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2020/067523 | 6/23/2020 | WO |
