Patent Grant
11563212
This application is a National Stage of International Application No. PCT/EP2018/063373 filed May 22, 2018, claiming priority based on French Patent Application No. 1755608 filed Jun. 20, 2017.
The technical field of the invention is that of electrochemically active materials intended for use in the positive electrode (or cathode) of a rechargeable electrochemical cell (or battery) of the lithium-ion type.
The operation of a lithium-ion electrochemical cell is based on the principle of reversible insertion of lithium into a host structure of an electrochemically active material. When the cell is charged, the electrochemically active material of the positive electrode oxidizes and extracts lithium from its structure while the electrochemically active material of the negative electrode reduces and lithium is inserted into its structure. Conversely, when the cell is discharged, the electrochemically active material of the positive electrode reduces and inserts lithium into its structure, while the electrochemically active material of the negative electrode oxidizes and lithium extracts from its structure.
Graphite is commonly used as an electrochemically active material in the negative electrode of a lithium-ion cell. When the cell is first charged, a passivation layer on the surface of the negative electrode is formed by decomposition of the electrolyte contained in the cell. Its formation is necessary because it avoids the exfoliation of graphite, leading to a high irreversible capacity, by preventing the co-intercalation of solvent. This passivation layer consumes lithium which will no longer be used to insert and extract and will therefore not participate in subsequent discharges. It is the cause of an irreversible capacity of the negative electrode.
At the positive electrode, during the discharge of the electrochemical cell, a fraction of the lithium does not re-enter the structure of the electrochemically positive active material. This unused fraction constitutes the irreversible capacity of the positive electrode.
Some lithium-ion electrochemical cells are characterized by an irreversible capacity of the negative electrode greater than that of the positive electrode. Examples include:
electrochemical cells comprising a graphite-based negative electrode and a positive electrode based on LiCoO2, or based on a lithium nickel manganese cobalt oxide (NMC), or based on a lithium nickel cobalt aluminium oxide (NCA), or based on LiFePO4 or
electrochemical cells the negative electrode of which is based on silicon, have an irreversible capacity which can reach up to 30 to 40%.
One of the consequences of the existence of this difference in these irreversible capacities is the non-use of part of the capacity of the electrode with the lowest irreversible capacity. The energy density of the electrochemical cell is then lower than that of a cell the irreversible capacities of which would be identical for both electrodes. This problem is illustrated in
Different ways have been sought to reduce the difference between the irreversible capacity of the positive electrode and the irreversible capacity of the negative electrode. Irreversible capacities can be artificially equalized either by pre-charging the negative electrode, for example by adding lithium metal, or by adding an active material of high irreversible capacity, also called sacrificial positive material, to the positive electrode. In the latter case, the use of an active material with a high irreversible capacity makes it possible to lighten the positive electrode since, compared to an active material with a low irreversible capacity, it is sufficient to use a smaller mass of active material for a given irreversible capacity.
Different sacrificial positive active materials are known. Examples include:
Document WO 2015/011883 describes a sacrificial positive active material of the formula Li6MnO4, or (Li2O)0.75(MnO)0.25. The disadvantage of this active material is that it must be charged to a high potential, i.e. higher than 4.4V compared with lithium metal. The charging potential indicated in FIG. 8 of document WO 2015/011883 is indeed 4.5 V. Such a potential is detrimental to the life of the electrochemical cell. On the other hand, this figure shows that for a charging voltage of 4.4V, the charged capacity is less than 450 mAh/g. For a charging voltage of 4V, the charged capacity is less than 100 mAh/g, which is very low. What is sought, therefore, is a sacrificial positive active material with a higher charged capacity and for a charge potential with respect to lithium not exceeding 4.4V.
The invention proposes novel compounds that can be used as sacrificial positive active materials. These compounds have a high irreversible capacity, preferably from 630 mAh/g to about 1200 mAh/g.
A first object of the invention is a compound of the formula
(Li2O)x(MnO2)y(MnO)z(MOa)t
wherein
x+y+z+t=1
1−x−y≥0
0.97≥x≥0.6
y≤0.45·x−0.17
y≥0
y+z>0
t≥0
1≤a<3
M is selected from the group consisting of Fe, Co, Ni, B, Al, Ti, Si, V, Mo, Zr and a mixture thereof.
This compound can crystallize in the cubic system.
It can present an X-ray diffraction pattern, in which the width at mid-height of the line at a 2-theta angle between 40° and 45° is greater than 1°, the wavelength used being the Kalpha wavelength of copper.
According to an embodiment, x≥0.7, preferably x≥0.8, preferably still x≥0.9.
According to an embodiment, y=z+/−0.05.
According to an embodiment, y≤0.2, preferably y≤0.1.
According to an embodiment, z≤0.4, preferably z≤0.3, preferably still z≤0.2, preferably still z≤0.1.
According to an embodiment, t=0.
A second object of the invention is a composite material comprising the compound as described above and a Li2O crystalline phase.
This composite material can contain from 1 to 10% by mass of carbon.
A third object of the invention is an electrode comprising a first sacrificial electrochemically active material which is the compound as described above and at least one second electrochemically active material.
According to an embodiment, the second electrochemically active material is chosen from the group consisting of:
According to an embodiment, the electrode comprises the compound ii) and
M is Ni;
M′ is Mn;
M″ is Co and
M′″ is selected from the group consisting of B, Mg, Al, Si, Ca, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb and Mo;
with 0.8≤x≤1.4; 0<y≤0.5; 0<z≤0.5; 0≤w≤0.2 and x+y+z+w<2.
According to an embodiment, the electrode comprises the compound ii) and
M is Ni;
M′ is Co;
M″ is Al; and
1≤x≤1.15;
y>0;
z>0;
w=0.
According to an embodiment, the electrode comprises the compound ii) and x=1; 0.6≤2−x−y−z≤0.85; 0.10≤y≤0.25; 0.05≤z≤0.15.
According to an embodiment, the electrode comprises the compound ii) of formula LiCoO2.
According to an embodiment, the electrode comprises compound iv). Preferably, compound iv) has the formula LiFePO4.
According to an embodiment, the electrode comprises the compound iii) with x=1; 0≤y≤0.1; z=0 and M′ is Al. The compound iii) may have the formula LiMn2O4.
According to an embodiment, the mass percentage of the compound as described above is less than or equal to 5% of the total mass of all electrochemically active materials, preferably less than or equal to 2%.
A fourth object of the invention is an electrochemical cell of the lithium-ion type comprising a positive electrode as described above.
According to an embodiment, the electrochemical cell comprises:
According to an embodiment, the electrochemical cell comprises:
Finally, a fifth object of the invention is a process for manufacturing the compound as described above, said process comprising the steps of:
a) provision of a mixture of Li2O, MnO, MnO2 and optionally MO;
b) grinding the mixture in an inert atmosphere;
c) heating the mixture in an inert atmosphere at a temperature between 800 and 1000° C.;
d) cooling of the mixture to room temperature;
e) grinding the mixture in an inert atmosphere;
f) possibly adding carbon to the mixture;
g) possibly grinding the mixture in an inert atmosphere.
The compound according to the invention has the formula
(Li2O)x(MnO2)y(MnO)z(MOa)t
wherein
x+y+z+t=1
1−x−y≥0
0.97≥x≥0.6
y≤0.45·x−0.17
y≥0
y+z>0
t≥0
1≤a<3
M is selected from the group consisting of Fe, Co, Ni, B, Al, Ti, Si, V, Mo, Zr and a mixture thereof.
This formula defines a composition range. This composition range can be represented in a ternary diagram. Assuming that cell M is absent from the compound, the formula of the compound according to the invention can be rewritten:
(Li2O)x (MnO2)y (MnO)z. The three pure components Li2O, MnO2 and MnO are the three vertices of this ternary diagram.
Five criteria are imposed on parameters x, y and z. They define the composition range of the compound according to the invention in the ternary diagram. These criteria are as follows:
Criterion 1: x≥0.6
Criterion 2: y≤0.45·x−0.17
Criterion 3: x≤0.97
Criterion 4: y+z>0
Criterion 5: 1−x−y≥0
The applicant found that the theoretical capacity of the compound according to the invention increased with the Li2O content. Therefore, x is preferably greater than or equal to 0.7, preferably still x is greater than or equal to 0.8, preferably still x is greater than or equal to 0.9.
The applicant also found that when the quantity of MnO is close to that of MnO2, a high capacity was obtained. “Close to” means y=z±0.05. In the ternary diagram in
According to a preferred embodiment, the compound according to the invention is devoid of the cell M, i.e. t=0.
The compound according to the invention is generally nanostructured. The size of the crystallites is typically less than 50 nm, preferably less than or equal to 10 nm, preferably even less than or equal to 5 nm. This nanostructure can be demonstrated by using the X-ray diffraction technique. The X-ray diffraction pattern on a powder of the compound has a peak at a 2-theta angle between 40° and 45°, the width at mid-height of which is greater than 1°. The wavelength used for the measurement is the Kalpha wavelength of copper. The width at mid-height can be greater than or equal to 2°, greater than or equal to 3°. It has been observed that the width at mid-height of the peak increases as the size of the crystallites decreases. Typically, a width at mid-height peak of about 2° corresponds to a crystallite size of about 5 nm.
The compound according to the invention generally crystallizes in the cubic system. The cubic system can be demonstrated by using the Rietveld refinement method which uses the X-ray diffraction technique.
A second Li2O phase is usually present with the compound of the invention. The X-ray diffraction pattern characteristic of the presence of the Li2O phase has peaks at the following 2-theta angles: 34°, 39°, 56°, 71° and 84°±1°, the angle being obtained using the Kalpha wavelength of copper.
The compound according to the invention is generally used in mixture with at least one second electrochemically active material. This second electrochemically active material can be selected from the group consisting of:
The compound according to the invention may be used in combination with one or more electrochemically active materials which may or may not be part of compounds i) to v).
In an embodiment, the lithium-ion electrochemical cell comprises:
Generally, carbon is mixed with the compound according to the invention and any other electrochemically active material present in the positive electrode. The mass proportion of carbon used generally represents 3 to 10% of the sum of the masses of the positive active materials.
The process used to obtain the compound according to the invention is a mechanical alloying process. Mechanical alloying refers to all material techniques in which the energy for activating the chemical reaction between precursors is provided by mechanical means. The manufacturing process includes the steps of:
a) provision of a mixture of Li2O, MnO, MnO2 and optionally MO;
b) grinding the mixture in an inert atmosphere;
c) heating the mixture in an inert atmosphere at a temperature between 800 and 1000° C.;
d) cooling of the mixture to room temperature;
e) grinding the mixture in an inert atmosphere;
f) possibly adding carbon to the mixture;
g) optionally grinding the mixture in an inert atmosphere if carbon has been added in step f).
According to an embodiment, step c) of heating is carried out for a period of 3 to 5 hours.
Preferably, step c) of heating the mixture is carried out at a temperature ranging from 850 to 950° C., preferably 900° C., for a period ranging from 3.5 h to 4.5 h, preferably 4 h. The temperature rise to the desired temperature is carried out gradually over a period of 4 to 6 hours, preferably 5 hours.
Preferably, step d) of cooling to room temperature is carried out gradually over a period of 4 to 6 hours, preferably 5 hours.
According to an embodiment, step e) of grinding the mixture is carried out for a period of 13 to 17 hours.
Preferably, step e) of grinding the mixture is carried out over a period of about 15 hours.
According to an embodiment, step g) of grinding the mixture is carried out for a period of 4 to 6 hours.
The process according to the invention makes it possible to obtain a stabilization of the cubic phase as well as a nanostructuring of the compound.
Thirteen examples of compounds according to the invention have been synthesized. Their composition is shown in Table 1 below. The procedure used to synthesize them is as follows:
First, the precursors Li2O, MnO, MnO2 and MO, if applicable, were ground in a mortar in stoichiometric proportions in a glove box under argon atmosphere (total mass of precursors: 5 g). Then, a heat treatment in a sealed tube was carried out for 4 hours at 900° C. The temperature rise to 900° C. occurred in 5 hours, as did the temperature drop to 25° C.
The resulting material was then ground for 15 hours under argon atmosphere, in 10 mL WC tungsten carbide bowls with 4 WC balls 10 mm in diameter, using a FRITSCH™ planetary mill. The grinding speed is 700 rpm. After 5 hours, 10 hours and 15 hours, the grinding was stopped and the walls of the bowl were scraped in the glove box to homogenize the powder which is compacted on the walls. In order to avoid heating during the 5 consecutive hours of grinding, ten 30-minute cycles with a 5-minute break were carried out, alternating the direction of rotation of the grinding bowls.
Carbon was added to the material already ground for 15 hours at a rate of 5% by mass with respect to the mass of the material already ground for 15 hours. Then, the mixture containing the carbon was ground again for a further 5 hours, under the same conditions as before (10 cycles of 30 minutes at a speed of 700 rpm, alternating the direction of rotation of the grinding).
xLi2O
yMnO2
zMnO
tMOa
The position of compounds 1-10 in a ternary diagram is shown in
The compound of example 1 of formula Li9MnO6 was studied for its crystallographic structure. An X-ray diffraction pattern was performed on a powder of this compound. It is shown in
The compound of example 7 of formula Li10Mn2O7 was also studied for its crystallographic structure. An X-ray diffraction pattern was performed on a powder of this compound. It is shown in
For comparison, the compound Li6MnO4 described in document WO 2015/011883, cited in the discussion of prior art, is not nanostructured. Indeed, referring to FIG. 14 of document WO2015/011883, it can be noted that the peak at a 2-theta angle between 40 and 45° has a half-height width of less than 0.3°, which means that the size of the crystallites is greater than 50 nm.
Electrical Tests:
The electrical tests were performed using Swagelok®-type laboratory electrochemical cells. The positive electrode has a surface area of 1.14 cm2 and consists of from 20 to 30 mg of a mixture comprising 72% by mass of electrochemically active material and 28% by mass of carbon. The mixture was previously mixed with the FRITSCH™ planetary mill for 30 minutes at 450 rpm. The negative electrode consists of a lithium disc in large excess of capacity compared with the positive electrode. The thickness of the lithium disc is 500 μm. The two electrodes are electrically isolated by two layers of borosilicate glass fibre (Whatman™) separators. The electrolyte used is composed of 1 M LiPF6 dissolved in a mixture of ethylene carbonate and methyl ethyl carbonate EC:MEC in a mass ratio of 3:7.
The charge currents were calculated to extract one Li atom per compound formula in 20 hours.
The cut-off voltage of the first charge is 4.4V and 1.2V for the discharge.
The cut-off voltage of the second charge is 4.6V and 1.2V for the discharge.
The cut-off voltage for the third charge is 4.8V and 1.2V for the discharge.
The results of the electrical tests are summarized in Table 2 below
xLi2O
yMnO2
zMnO
tMOa
Table 2 shows that the compounds according to the invention have, for a charging voltage of 4.4V, a total charged capacity of at least 630 mAh/g, up to 1200 mAh/g.
The galvanostatic cycling of the compound in example 1 of formula Li9MnO6, in half-cell versus lithium (Swagelok® type) was performed. The resulting cycling curve is shown in
The galvanostatic cycling curve of the compound in example 7 of formula Li10Mn2O6, in half-cell versus lithium (Swagelok® type) is shown in
Compounds not part of the invention were synthesized and their capacity were measured. The position of these compounds in a ternary diagram is shown in
xLi2O
yMnO2
zMnO
tMOa
Table 3 shows that the counter-examples have, for a charging voltage of 4.4V, a total charging capacity not exceeding 620 mAh/g. None of these compounds meet all five criteria.
Validation in Mixture with a Cathode Active Material with Low Irreversible Capacity LiFePO4:
The validation of the invention was carried out by comparing two positive electrodes, one based on LiFePO4 (electrode A) and the other by replacing 2% of this compound with the Li9MnO6 compound of 1125 mAh/g capacity (electrode B). This substitution creates an irreversible capacity of about 20 mAh/g of positive active material.
The reference electrode A was manufactured with the following mass composition: 77% LiFePO4/23% carbon.
The electrode B according to the invention was manufactured with the following mass composition: 75.5% LiFePO4/1.5% Li9MnO6/23% carbon. The mass of Li9MnO6 represents about 2% of the sum of the masses of positive active materials.
The mixture of active material(s) and carbon is deposited on a current collector of the positive electrode at a rate of 12.65 mg/cm2.
The electrical tests performed on both electrodes are as follows:
1: Charging at a rate allowing to extract a Li atom by compound formula in 20 hours, up to 4V.
2: Constant voltage charging supplement (4V) with an end of charge current corresponding to C/1300
3: Discharge up to 2V at a C/10 rate
The charge-discharge curves for each of these electrodes have been plotted. They are shown in
The total charged capacity during the first charge for electrode A is 165 mAh/g and that of electrode B is 185 mAh/g. The capacity measured during the first discharge is the same for both electrodes, which means that the irreversible capacity has been increased by 20 mAh/g as expected.
The increase in the mass capacity of an electrochemical cell of the lithium-ion type by the use of a compound according to the invention in the positive electrode can be verified by calculation. The assumptions used are as follows:
A reference electrochemical cell R comprises:
LiFePO4 used in the two cells R and I described above has a total mass capacity of 165 mAh/g, of which 9% is the irreversible mass capacity, or 15 mAh of irreversible capacity.
The C/Si composite used in the two cells R and I described above has a total mass capacity of 1266 mAh/g, of which 21% is the irreversible mass capacity, or 266 mAh/g of irreversible capacity.
The Li9MnO6 compound has a total mass capacity of 1125 mAh/g.
On the basis of the numerical values of the capacities described above and the assumption that the total capacity of the negative electrode is equal to the total capacity of the positive electrode, the mass capacity of the cells R and I expressed per gram of positive and negative material can be calculated. The results of this calculation are shown in Tables 4a and 4b below:
Table 4b shows that the capacity of cell I is 128 mAh per gram of positive and negative active materials while that of cell R is only 115 mAh/g, representing a mass capacity gain of about 10%.
The capacities of the positive and negative electrodes of the reference cell R are shown schematically in
The capacities of the positive and negative electrodes of cell I according to the invention are shown schematically in
The comparison of
| Number | Date | Country | Kind |
|---|---|---|---|
| 1755608 | Jun 2017 | FR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2018/063373 | 5/22/2018 | WO |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2018/233963 | 12/27/2018 | WO | A |
| Number | Name | Date | Kind |
|---|---|---|---|
| 20130323597 | Levy | Dec 2013 | A1 |
| Number | Date | Country |
|---|---|---|
| WO 2015-011883 | Jan 2015 | WO |
| Entry |
|---|
| Buzanov et al, “Isothermal Diagrams of the Li2O—MnO—MnO2 System”, Doklady, Chemistry, Maik Nauka/Internperiodica Publishing, Moscow, RU, vol. 465, No. 1, 5, 2015, pp. 268-271. |
| English translation of WO Publication 2015-011883, Jan. 2015. |
| Number | Date | Country | |
|---|---|---|---|
| 20200136140 A1 | Apr 2020 | US |
