Patent Grant
10899648
The invention relates to an electrolyte or an electrolyte additive which in particular can be used in lithium-ion batteries or other battery designs, such as lithium-air batteries or lithium-sulfur batteries.
Lithium-ion batteries and future battery designs, such as lithium-air batteries or lithium-sulfur batteries apart from a high energy density must fulfill also high demands with respect to safety and reliability which must be ensured for the total life-time. In this regard liquid electrolytes in the past often have emerged negatively, since they have the tendency to dissolve which may lead to a loss in conductivity and/or to undesired disintegration products, and since they are easily flammable.
An alternative are polymeric electrolytes which however have only small ionic conductivities. By contrast, gel-electrolytes, which are a combination of liquid and polymeric electrolytes, often have better conductivities, however have the tendency to be flammable.
Due to this reason it has been tried for a long time to develop solid electrolytes as an alternative. With respect to solid electrolytes an ionic conductivity of at least 10−5 S/cm, better at least 10−4 S/cm is demanded. At the same time the electronic conductivity should be lower by at least 4 to 5 magnitudes to avoid a self-discharging of the battery. In addition the chemical resistance against all materials used in the battery is expected, in particular against metallic lithium. Of course, also a sufficient electrochemical stability during charging and discharging (cycling) of the battery should be present.
Such demands are fulfilled only by few known materials. These include on the one hand sulfidic systems with the main components lithium, phosphorus and sulfur, and on the other hand oxidic systems with NaSiCon or garnet-like crystal phases.
Sulfidic compositions such as Li—S—P, Li2S—B2S3—LI4SiO4 or Li2S—P2S5—P2O5Li—S—P, and Li2S—P2S5—P2O5 often are prepared by grinding the starting ingredients under protective gas and by a subsequent temperature treatment (usually also under protective gas) (confer to this end US 2005/0107239 A1, US 2009/0159839 A1). Partially ionic conductivities of more than 10−3 S/cm are reported at room temperature.
However, the large-scale production of such materials is complicated, since it must be performed in the absence of air, since the materials are not stable under air. In particular, the presence of only small amounts of water has been found to lead to a fast disintegration. This leads to an increase of the production and processing cost and poses a safety-technical problem.
Also with oxidic systems with NaSiCon conductivities of more than 10−4 S/cm can be reached at room temperature.
However, the NaSiCon materials usually are not stable against metallic lithium which requires the utilization of an additional protective layer for protecting the anode (confer EP 1673818 B1). In addition for high conductivities often the use of costly row materials, such as germanium, tantalum or gallium is required.
An alternative are systems with garnet-like crystal phases, such as Li7La3Zr2O12 (US 2010/0047696 A1). From DE 10 2007 030604 A1 and from WO 2005/085138 A1 garnet-like crystal phases (Li7+xAx G3−xZr2O12 (with A: bivalent cation, G: trivalent cation) or Li5+xAxG3−xM2O12 (with A: bivalent cation, G: trivalent cation, M: pentavalent cation) are known. In the pure system Li7La3Zr2O12 at about 150 to 200° C. a reversible phase transition occurs from the tetragonal garnet phase, which is stable at room temperature, to the cubic garnet phase. The tetragonal garnet phase offers a lithium-ion conductivity of about 1.6×10−6 S/cm (confer J. Akawa et al., Journal of Solid State Chemistry 182 (2009), 2046-2052). The cubic phase which can be stabilized by means of dopings, such as with aluminum or tantalum also at room temperature, even shows a conductivity in the order of 10−4 S/cm (confer EP 2 159 867 A1).
Materials with lithium-garnet-like crystal phases usually are prepared by means of a solid body sintering route which often requires several grinding and several temperature treatment operations (confer EP 2 159 867 A1).
A problem with this production are the high temperatures up to about 1250° C. that are necessary for generating the desired crystal phases which at the same time lead to a strong lithium evaporation. The use of a too high lithium proportion leads to a stabilization of the tetragonal phase having poorer conductivity, while a lithium proportion that is too small leads to the generation of foreign phases. This complicates the preparation of highly conductive pure phase material on an industrial scale.
From DE 10 2012 207 424 B3 an ion-conducting, alkaline containing glass ceramic is known wherein after a ceramizing of the glass ceramic from a starting glass at least a part of the alkali-ions of the glass ceramic are exchanged against alkali-ions of a different, preferably smaller, atomic number. The glass ceramic comprises nepheline or carnegeit as main crystal phases and before the alkali-ion-exchange comprises at least the following components: 15-75 wt.-% SiO2, 4-60 wt.-% Al2O3, 4-65 wt.-% Na2O, 0-10 wt.-% Li2O, 0-10 wt.-% TiO2, 0-10 wt.-% ZrO2, 0-5 wt.-% SnO2, 0-20 wt.-% B2O3, 0-30 wt. % P2O5. The glass ceramics are molten within a platinum-rhodium crucible by melting the starting materials at 1600 to 1650° C., refining and stirring, thereafter casting, and are then controlled transferred into a glass ceramic according to a ceramization program. The glass ceramic comprises nepheline (NaAlSiO4) as a dominating phase and as side phases depending on the composition Na2TiSiO5, Li2SiO3, Li2TiO3. In a LiNO3 bath (6 hours at 340° C.) the sodium almost fully is exchanged against lithium. The lithium-ion conductivity is in the range of about 10−4 S/cm. The key part of such a glass ceramic shall be crystal phases of one or more crystal types within which alkali-ions can move relatively free on percolating paths, partially in veritable channel structures within a generated network within fixed bindings of mostly covalent character. It should be noted that such networks in particular can be designed using polyvalent cations, in particular trivalent to pentavalent cations with connecting oxygen atoms. Such crystal types shall be found in many crystal systems, such as in the perovskite-type lithium-lanthanum-titanate La(2/3−x)Li3×TiO3, sodiumbeta-aluminate NaAl11O17, borates, phosphates, chain, band, layer and framework silicates. In this context also the garnet-like Li5La3(Nb, Ta)2O12 is mentioned (confer Philippe Knauth: Inorganic solid Li ion conductors: An overview, Solid State Ionics 180 (2009) 911-916). However, with respect to the preparation nothing is disclosed in this regard.
In view of this it is a first object of the invention to disclose a material which is suitable as a solid-state electrolyte or as an electrolyte additive within a lithium-ion battery, an all-solid-state battery, a lithium-air battery, a lithium-sulfur battery, or another battery.
It is a second object of the invention to disclose a method of producing such a material on a technological scale in a simple and cost-effective way.
It is a third object of the invention to disclosed an improved battery having longer service life or increased capacity.
According one aspect of the invention this object is solved by a lithium-ion conducting glass ceramic with garnet-like main crystal phase having an amorphous proportion of at least 5 wt.-%, preferably at least 10 wt.-%.
The object of the invention is fully solved in this way.
According to the present invention a glass ceramic is understood as a material that is prepared on a melting technological route that has been transferred into a glass ceramic by a subsequent specific temperature treatment.
The glass ceramic according to the invention comprises an amorphous proportion of at least 5 wt.-%. The conductivity is positively influenced by the amorphous proportion. However, the proportion of the amorphous phase should be no larger than 40 wt.-%, preferably smaller or equal to 30 wt.-%, since otherwise the total conductivity is reduced.
A further advantage in the preparation of the glass ceramic rests in the possibility that the structure can be directly influenced by a specific crystallization, whereby the conductivity can further be influenced positively.
The glass ceramic according to the invention preferably has an ion-conductivity of at least 5·10−5 S/cm, preferably of at least 1·10−4 S/cm. Partially the ion-conductivity can be considerably higher.
The glass ceramic according to the invention comprises a garnet-like main crystal phase, preferably according to the chemical formula: Li7+x−yMxIIM3−xIIIM2−yIVMyVO12, wherein MII is a bivalent cation, MIII is a trivalent cation, MIV is a tetravalent cation, MV is a pentavalent cation, wherein preferably 0≤x<3, further preferred 0≤x≤2, 0≤y<2, and particularly preferred 0≤y≤1.
The glass ceramic for instance comprises preferably the oxides of lithium, lanthanum and zirconium, as well as further doping materials that make possible the stabilization of the cubic garnet phase at room temperature and that positively influence further characteristics, such as the meltability, the processing or the electrochemical characteristics, as desired.
As far as within this application compositions are given in the form that particular components are present therein or that they comprise particular components, these are always to be understood so that any additional components may be contained therein (open composition).
In a further configuration of the invention the given compositions however are also be understood so that the respective components given are contained therein (closed composition) apart from unavoidable contaminations that are due to the nature of the glass manufacture. Depending on the purity of the raw materials that are used, such unavoidable contaminations are limited to a maximum of 1 wt.-%, preferably of 0.5 wt.-%, further preferred to 0.1 wt.-%, or even to 0.05 wt.-%.
As far as in this application compositions are given in the form that they consist of particular components, then these compositions are always to be understood that only the given components are contained therein (closed composition), however with the proviso that unavoidable contaminations that are due to the nature of the glass manufacture, may be contained therein. Depending on the purity of the used raw materials, such unavoidable contaminations are limited to a maximum of 1 wt.-%, preferably of 0.5 wt.-%, more preferred of 0.1 wt.-%, or even of 0.05 wt.-%.
As far as within this application compositions are given in examples by listing particular components, these statements are to be understood as closed compositions, however with the proviso that unavoidable contaminations that are due to the nature of the glass manufacture, may be contained therein. Depending on the purity of the used raw materials such unavoidable contaminations are limited to a maximum of 1 wt.-%, preferably of 0.5 wt.-%, further preferred of 0.1 wt.-%, or even of 0.05 wt.-%.
Preferably the glass ceramic comprises 10-25 wt.-% Li2O, particularly preferred 10-20 wt.-% Li2O.
Further preferred the glass ceramic comprises 40-60 wt.-%, particularly preferred 50-60 wt.-% of an oxide of at least one lanthanoid, preferably La2O3.
According to a further development of the invention the glass ceramic comprises 15-35 wt.-%, preferably 15-30 wt.-%, further preferred 20-30 wt.-% of ZrO2.
With these raw materials the desired main crystal phase can be realized in a particularly simple and cost-effective way.
By the addition of further doping materials according to the above-given chemical formula in addition specific mixed crystal main phases can be produced, whereby the conductivity can be further optimized.
The glass ceramic according to a further development of the invention preferably comprises 0-10 wt.-%, further preferred 0-5 wt.-%, further preferred 1-5 wt.-% of an oxide selected from the group consisting of Al2O3, Bi2O3, Ga2O3, Y2O3, Fe2O3, Cr2O3, In2O3, and mixtures thereof.
According to a further development of the invention the glass ceramic preferably comprises 0-20 wt.-%, further preferred 1-20 wt.-%, further preferred 0-13 wt.-%, further preferred 1-13 wt.-%, particularly preferred 5-13 wt.-% of an oxide selected from the group consisting of Ta2O5, Nb2O5, V2O5, P2O5 and mixtures thereof.
According to a further development of the invention the glass ceramic preferably comprises 0-10 wt.-%, further preferred 0-5 wt.-%, particularly preferred 1-5 wt.-% of an oxide selected from the group consisting of TiO2, HfO2, SnO2, and mixtures thereof.
According to a further development of the invention the glass ceramic preferably comprises 0-10 wt.-%, further preferred 1-10 wt.-%, at least of an oxide selected from the group consisting of RO, ZnO and mixtures thereof, wherein R is an alkaline earth ion.
By these additions the desired characteristics can be further positively influenced, that is in particular the conductivity can be increased, the chemical stability against the materials used within the battery can be positively influenced, and partially also the production during melting is simplified. In addition, a sufficient electrochemical stability during cycling of the battery can be positively influenced.
The glass ceramic according to the invention preferably is used as an electrolyte or an electrolyte additive within a lithium-ion battery, an all-solid-state battery, a lithium-air battery or a lithium-sulfur battery.
Also the application of the glass ceramic as an electrode additive in such a battery is conceivable.
All known integration forms are possible, such as a thin layer or membrane, as single electrolyte or as a component of the electrolyte together with a different material. For preparing such a layer or membrane apart from the shaping possibilities of a glass (melting, tearing, rolling etc.) also techniques such as screen printing, foil casting or coating techniques may be utilized.
Also a utilization as a coating on an electrode is possible, such as a component of a composite electrolyte, preferably of a polymeric solid-state membrane. The glass ceramic may also be used as a component of a coating, wherein the glass ceramic preferably represents 50 to 100 vol.-%, further preferred 70 to 95 vol.-%, particularly preferred 80 to 90 vol.-% of the coating.
A glass ceramic according to the invention can be prepared by melting and homogenizing of the starting materials and by a cooling of the melt (preferably after a casting), by direct solidification or by a controlled cooling, or after quenching, followed by a temperature treatment (ceramization treatment) into a glass ceramic material with garnet-like main crystal phase.
Preferably, the melting and homogenizing is performed within an inductively heated Skull crucible.
Since lithium-containing glass melts are very aggressive, a melting within a platinum or platinum-rhodium crucible may at most be performed on a laboratory scale. A melting within a platinum crucible leads to an attack onto the crucible material and to detectable fractions of the noble material within the produced product. This again leads to a considerable increase in electronic conductivity which has a detrimental effect.
A further possibility for the production by melting technology is the utilization of a glass-carbon crucible. However, since these crucibles at the necessary high temperature are oxidized under oxygen-containing atmosphere, the production must be performed under protective atmosphere (nitrogen or argon). These production method is thus suitable for smaller lots, however is detrimental for a large-scale production, since linked to additional cost.
The melting and homogenizing within an inductively heated Skull crucible is thus a preferred production method, whereby the afore-mentioned disadvantages are avoided.
With respect to the details of the melting within the Skull crucible reference is made to DE 199 39 780 A1 and DE 199 39 782 C1 which are fully incorporated herein by reference.
Preferably, herein a Skull crucible is used which is made of a plurality of metal tubes which are traversed by a coolant having slot-like intervals between the metal tubes, and further having an induction coil surrounding the metal tubes from the outside, wherein the metal tubes preferably are shortened with each other.
It will be understood that the afore-mentioned features and to be described hereinafter cannot only be used in the respectively given combination, but also in different combinations or independently, without leaving the scope of the present invention.
Further features and advantages of the invention can be taken from the subsequent description of preferred embodiments with reference to the drawings. In the drawings show:
A glass ceramic according to the invention preferably has the garnet-like main crystal phase according to the chemical formula:
Li7+x−yMxIIM3−xIIIM2−yIVMyVO12,
wherein MII is a bivalent cation, MIII a trivalent cation, MIV a tetravalent cation, MV a pentavalent cation, wherein preferably 0≤x<3, more preferred 0≤x≤2, 0≤y<2, and particularly preferred 0≤y≤1.
The melting is performed within a so-called Skull crucible, such as described in DE 199 39 782 C1.
In the Skull technology a water-cooled crucible is utilized, within which during the melting a cooler protective layer forms from the molten material. Thus, during the melting procedure no crucible material is dissolved. The energy introduction into the melt is realized by coupling using high frequency coupling via the surrounding induction coil into the liquid material. A condition in this regard is a sufficient conductivity of the melt which in the case of lithium-garnet melts is ensured by the high lithium content. During the melting procedure there is a lithium evaporation which can easily be corrected by a lithium excess. To this end usually there is worked with a 1.1- to a 2-fold lithium excess.
The raw materials according to the composition given in TABLE 1 are mixed and then given into the Skull crucible that is open on the top side. The mixture had initially to be preheated to reach a certain minimum conductivity. To this end a burner heating was utilized. After reaching the coupling temperature the further heating and homogenizing of the melt was ensured by high frequency coupling via the induction coil.
To improve the homogenization of the melt, it was stirred using a water-cooled stirrer.
After full homogenization direct samples were taken from the melt (fast cooling), while the reminder of the melt was cooled slowly by switching off the high frequency.
The material prepared in this way may basically be either directly solidified from the melt or by quenching, followed by a temperature treatment (ceramizing) transferred into a glass ceramic material with garnet-like main crystal phase.
The samples taken from the melt independently from the cooling showed a spontaneous crystallization, so that a subsequent ceramization treatment could be dispensed with.
The measurement of the ion-conductivity showed the positive influence of the amorphous phase contained within the glass ceramic which can be explained by a reduction of the conductivity decrease by the grain boundaries.
From the glass ceramics obtained in this way samples for the impedance-spectroscopy were prepared for determining the conductivity, as well as for X-ray diffraction investigations (XRD). To avoid a degradation of the samples upon contact with water the sample preparation was performed water-free.
The X-ray diffraction investigations (XRD) in all samples showed a mixture of tetragonal and cubic crystal phases.
For a precise determining of the phase content a Rietveld-analysis was performed. According to TABLE 1 the samples that are doped with aluminum (no. 1-4) contain a fraction of cubic phase between 38 and 62%, while the samples that are doped with tantalum (nos. 5-8) contain a cubic fraction of 27 to 100% (each without taking into account the amorphous fraction). Also using a doping with niob makes possible a fully stabilization of the cubic phase (confer example 9).
Even in the samples with high tetragonal proportion there are considerably high conductivities. Thus example 3 that comprises 60% of tetragonal phase, the conductivity of which in literature is given with 1.6·10−6 S/cm, shows a conductivity of about 1·10−4 S/cm. This almost corresponds to the expected conductivity for aluminum-dopings of the pure cubic phase (2·10−4 S/cm).
A determination of the amorphous proportion using Rietveld-improvements, or using an external standard, respectively, with respect to the samples did not lead to correct results, due to the strong reflex superimpositions of the cubic and tetragonal LLZO phases. The determination of the amorphous proportion, or the crystallinity, respectively, therefore was made by evaluating the underground. Also measurements on fully crystalline samples show a noise which is due to crystal lattice flaws, the influence of optical devices, fluorescence effects and dispersive effects. If the sample is not fully crystalline, then to this noise the contribution of the amorphous phase is added. The constant noise therefore was determined using standard samples with defined amorphous proportions. In this way the determination of the amorphous proportion within the samples was made possible which is between 10 and 21% according to TABLE 1.
If the different conductivities of the cubic and tetragonal phases are taken into account, as well as the fact that in part considerable amounts of tetragonal phases are contained within the samples, then it can be derived that the amorphous phase contained within the glass ceramic increases the total conductivity which is a surprising result.
Since the determination of the amorphous proportion is done only indirectly, a sample (composition according to example 5) was examined using a polarization microscope. Herein dark regions are found within the sample which is evidence of an amorphous proportion.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10 2014 100 684 | Jan 2014 | DE | national |
This application is a division of U.S. application Ser. No. 15/215,421 filed on Jul. 20, 2016, which is a continuation of International Application PCT/EP2015/050889 filed on Jan. 19, 2015, which claims priority from German Application 10 2014 100 684.4 filed on Jan. 22, 2014, the entire contents of all of which are incorporated herein by reference.
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| Number | Date | Country | |
|---|---|---|---|
| 20200144660 A1 | May 2020 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 15215421 | Jul 2016 | US |
| Child | 16596588 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/EP2015/050889 | Jan 2015 | US |
| Child | 15215421 | US |
