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  • H01M4/139—Processes of manufacture
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  • H01M4/381—Alkaline or alkaline earth metals elements
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  • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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  • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
  • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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  • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
  • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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  • Y02E60/10—Energy storage using batteries
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the invention relates to a method for producing a rechargeable battery
• both the negative electrode (anode) and the positive electrode (cathode) consist of materials that can insert lithium ions without fundamental changes in the microstructure. While a carbon-based material - graphite or hard carbon - is used as the anode material, the cathode active materials consist of transition metal oxides. The transition metals in the latter oxides are redox-active, i.e. they change their oxidation state when loading or unloading. This is demonstrated by the following example reaction:
• LiM + l, l 0 2 Li + + e- + M + IV 0 2 M discharge metal, e.g. Ni, Co, Mn
• the oxidation level of the redox-active metal centers is only changed by one level when charging / discharging the battery, in the above case the oxidation levels change between +111 and +
• the theoretical capacity is 274 mAh / g, of which only approx. 135 mAh / g can be used in practice.
• the graphitic material used for the anode also has a relatively low capacity for the limit stoichiometry LiC6 with 372 mAh / g.
• the theoretical energy density for the graphite (C6) / LiCo0 2 system is also unsatisfactorily low and is around 380 Wh / g.
• Another disadvantage of lithium ion batteries lies in the fact that the cathode materials mainly used are those of the unavailable elements such as cobalt and nickel. There is a fear that the metals mentioned are insufficient Amount is available to ensure a nationwide supply of lithium batteries for worldwide electromobility and stationary energy storage.
• Open battery systems are being investigated as an alternative to cation redox active positive electrode materials. These contain a porous structure, usually made of carbon, which is open to the environment and the surface of which is covered with a noble metal-containing catalyst, so that diffused oxygen can be bound to form lithium oxides (oxygen reduction reaction):
• lithium superoxide L1O2
• the oxygen has an average oxidation number of -0.5. Further absorption of lithium produces lithium peroxide (L12O2) with an oxygen oxidation number of -1.
• the latter lithium oxide can be converted back into lithium and elemental oxygen in the presence of a metal catalyst catalyzing the oxygen oxidation, in reverse of the formation reaction:
• the air electrode described above has only a very moderate power density and, above all, only a very limited reversibility, so that this cathode shape is still a long way from being used in practical batteries.
• the current major technical challenges lead to the expectation that the lithium / air battery can be commercialized at the earliest in 10 - 20 years. For an overview, see K. Amine et al., Chem. Review 2014, 561 1 -40, 1 14.
• lithium oxides (L12O, L12O2 and L1O2) as active cathode materials that work according to the anion redox principle. Since all of the lithium oxygen compounds mentioned are electronic insulators, they must be in finely divided (amorphous or nanoparticulate) form or in a very thin layer and the individual particles must be contacted using a conductive network. In addition, there are, for example, conductive, finely divided metals as well as many metal oxides and lithium metal oxides. Such systems are known from the literature and only exemplary embodiments are mentioned here.
• Lithium peroxide (L12O2) can be contacted by cover grinding with mixed-conductive LiNio , 33 Coo , 33 Mno , 33 0 2 and completely decomposed cathodically (Y. Bie et al., Chem. Commun. 2017, 53, 8324-7).
• Composites consisting of a mixture of Co-Metall and L12O, both in nanoparticulate form, can also be completely decomposed cathodically (Y. Sun, Nature Energy, January 2016, 15008).
• the practical functionality of a full battery cell containing nanoparticulate lithium oxides (a mixture of U2O, L12O2 and L1O2), embedded in a matrix of Co 3 0 4 , is known (Z. Zhu, Nature Energy, 25 July 2016, 161 1 1).
• a charging voltage of about 3 - 3.5 V vs Li / Li + must not be exceeded.
• Lithium superoxide (L1O2) is not thermodynamically stable in crystalline form, but breaks down into L12O2 and oxygen (K.C. Lau, J. Phys. Chem. C 1 15, 23625-33).
• Lithium peroxide is a strong oxidizing agent and decomposes in contact with water with the evolution of oxygen. Both connections mentioned can therefore not be handled safely on a larger scale.
• Lithium oxide L12O although thermodynamically stable, is not commercially available. It is very caustic and can only be achieved using energy-intensive processes, e.g.
• the invention has for its object to provide a method for manufacturing and an electrochemical storage system that ensure a high enough energy density of at least 500 Wh / kg especially for mobile applications can. Furthermore, commercially available and safe to handle active materials with the lowest possible content of rare or poorly available metals are to be used.
• the object is achieved by a method for producing a rechargeable high-energy battery with an anion-redox-active composite cathode, in which the anion-redox-active composite cathode contains lithium hydroxide as an electrochemically active component, which is mixed and contacted with electronically or mixed conductive transition metals and / or transition metal oxides lies, so that an electronic or mixed-conductive network is formed, this mixture is applied to a current conductor and the composite cathode formed in this way is introduced into a cell housing together with a separator, a lithium-conductive electrolyte and a lithium-containing anode, so that a electrochemical cell is present. This is subjected to at least one initial forming cycle.
• the cathode contains lithium hydride (LiH) at least after the first discharge cycle (ie in the lithium-rich state).
• LiH arises according to one of the equations (1) to (3), see below.
• the electrochemically active constituents are embedded in an electronically or mixedly conductive network which contains transition metal particles and / or electronically conductive transition metal oxides and, if appropriate, further conductivity-improving materials.
• the lithium oxygen compound lithium hydroxide LiOH
• a further lithium oxygen compound selected from L1 2 O, L1 2 O 2 and L1O 2 Lithium hydroxide is commercially available and is easy and safe to use.
• the proportion of LiOH in the composite cathode material, based on the total content of the above-mentioned lithium oxygen compounds, is at least 10 mol%, preferably at least 30 mol%.
• the negative electrode (anode) contains at least one lithium-donating component or compound with an electrochemical potential of ⁇ 2 V against the Li / Li + reference electrode.
• the lithium-donating, electrochemically active component or compound is selected from metallic lithium, a lithium-containing metal alloy, a lithium nitrido transition metalate or composite materials, the electrochemically active component of which is a metal nitrogen compound, which is embedded in a transition metal-containing electronic or mixed-conductive network.
• the two electrodes When producing a rechargeable high-energy battery, preferably a secondary lithium battery, containing a composite cathode according to the invention and an anode, the active materials of which have an electrochemical potential of ⁇ 2 V against Li / Li + , the two electrodes must be properly balanced (i.e. weight-matched) with regard to the electrochemically active ingredients they contain.
• Proper balancing is characterized by the fact that the electrochemical active materials can be used as completely as possible.
• the anode contains a molar amount of electrochemically activatable lithium, i.e. electrochemically extractable from the anode, before the first discharge cycle, which contains at least half, preferably at least the same and particularly preferably at least twice the molar amount of the corresponds to the LiOH content of the composite cathode. This is explained below.
• lithium hydride (LiH) is formed in addition to lithium oxide (L12O), lithium peroxide (L12O2) and / or lithium superoxide (L1O2) in the first discharge cycle.
• LiH lithium hydride
• LiO2 lithium oxide
• L12O2 lithium peroxide
• L1O2 lithium superoxide
• the lithium oxide compound As a result of the first discharge reaction, in addition to lithium hydride, at least one lithium oxide compound is formed which is anion-redox active and which does so for the subsequent cycles represents electrochemically active cathode material used.
• the inventors have found that reactions (1) to (3) surprisingly only take place if adequate electronic or mixed electronic / ionic contacting of the lithium hydroxide particles is ensured.
• the lithium hydroxide particles should preferably be in finely divided form (nanoparticulate). The same also applies to any other lithium oxygen compounds present in the cathode material, selected from L12O, L12O2 and LiC> 2.
• reaction equation (1) with a molar ratio of 1: 2 between LiOH: extractable (i.e. electrochemically active) lithium, particularly preferred.
• the electrochemically active cathode material according to the invention in the lithium-rich form present after the first discharge cycle can in principle also be produced by mixing L12O and / or another lithium oxygen compound and LiH.
• this manufacturing variant is not particularly advantageous for practical reasons.
• Lithium hydride is namely not stable to reactive Heilbe components such as water vapor and carbon dioxide (decomposition to lithium hydroxide or lithium carbonate).
• lithium oxide is not commercially available and requires energy-intensive manufacturing processes.
• the cathode according to the invention contains lithium hydride at least after it has been discharged for the first time (ie in the lithium-rich state). Surprisingly, the lithium hydride formed in the first discharge cycle decomposes smoothly in the subsequent charge cycle, presumably according to the following reaction:
• Rechargeable lithium batteries require operation to prevent access to metallic lithium reactive gases and compounds.
• the air components oxygen, nitrogen, carbon dioxide, water vapor and other air trace components are reactive towards lithium.
• rechargeable lithium batteries generally have to be operated in the closed state (ie filled in a hermetically sealed housing).
• hydrogen gas is formed at least in the first charging cycle.
• the hydrogen formed is not reactive towards metallic lithium at moderate temperatures, but it would lead to an undesirable build-up of pressure within a hermetically sealed battery cell. In order to avoid this undesirable effect, at least the first and possibly further discharge / charge cycles must be carried out in the open state.
• the pressure equalization is generally carried out via an open capillary, which is closed after the gas-forming reaction or the gas-forming reactions have ended completely.
• the lithium formed in the first charging cycle migrates in a cationic form through the separator to the anode and separates there in the metallic state or reacts with substances or compounds present there which are capable of absorbing lithium.
• This can be an at least partially reversible reaction, such as, for example, with a graphitic material, a metal capable of absorbing lithium, a low-metal alloy, and low-lithium forms of lithium nitride transition metalates and / or composite materials, the electrochemically active component of which is a metal nitrogen compound, the metal nitrogen compound being a transition metal-containing compound electronic or mixed-conductive network is embedded.
• irreversible reactions such as, for example, electrolyte decomposition and / or the formation of a passivating layer on the surface of particulate or sheet-like constituents of the anode, in particular their electrochemically active components, can also be involved.
• the irreversibly consumed lithium in this way indirectly increases the gravimetric capacity of a rechargeable lithium battery cell, since otherwise lithium from another source, for example a lithium oxygen compound selected from L1 2 O, U 2 O 2 , L1O 2 and / or one other cathode material, such as a lithium transition metal oxide, must be used.
• the electrochemically active lithium compounds selected from lithium hydroxide (LiOH), lithium oxide (L12O), lithium peroxide (L12O2) and / or lithium superoxide (L1O2) and possibly lithium hydride (LiH) must be embedded in an electronically or mixed conductive network consisting of finely divided transition metal particles and / or finely divided conductive transition metal oxide compounds with an electrochemical potential (lithium intercalation potential) of> 2 V against Li / Li + . It is important that the closest possible contact between the electrochemically active lithium compounds and the transition metal or the conductive transition metal oxide compounds with an electrochemical potential> 2 V is guaranteed.
• the latter as well as the electronically or mixed-conductive transition metal oxide compounds with an electrochemical potential of> 2 V against Li / Li + are present in the finest possible distribution, ie amorphous or nanoparticulate form.
• the exact dimensions of the preferred nanoparticulate impression depend on the mechanical form factor (ie the three-dimensional shape of the particles). In the case of spherical (or similar) particle shapes, this is 0.1-100 nm, preferably 1-30 nm.
• the solid components of the cathode composite material can be comminuted by a grinding process, preferably using a high-energy mill, and brought into close contact with one another.
• a grinding process preferably using a high-energy mill
• nanoparticulate forms of the lithium oxygen compounds and the electronically or mixedly conductive transition metals or transition metal oxide compounds with an electrochemical potential of> 2 V against Li / Li + are obtained in this way.
• Nanoparticulate particle morphologies can also be produced by alternative physical (vapor deposition, plasma and laser methods) or chemical processes, for example solvent-based processes, preferably sol / gel processes.
• the molar ratio between the finely divided transition metals and / or the electronically or mixed-conductive transition metal oxide compounds on the one hand and the active materials based on lithium oxygen compounds selected from LiOH, L12O, L12O2 and L1O2 on the other hand in the cathode is in the range of 1: 100 to 1: 1, preferably 1:50 to 1: 1.5.
• the following metal oxide compounds are preferably used: binary metal oxides such as titanium oxides (TiO, T12O3), vanadium oxides (V2O3, VO, VO2), iron oxides (Fe 3 0 4 , FeO), cobalt oxides (C0O2, Co 3 0 4 ), nickel oxides (N12O3 ), Manganese oxides (Mn02, Mn 3 0 4 ), chromium oxides (Cr02, Cr 3 03), niobium oxides (NbO); layer-structured lithium metal oxides (L1C0O2, LiNiC> 2, Li (Ni, Mn, Co) C> 2), L1V3O8; Spinel-structured lithium metal oxides (LiMn20 4 , LiMnNi02, LiNio.5Mn1 5O4,, L1V3O5; inverse spinel-structured lithium metal oxides (UN1VO4, LiCoV0 4 ); olivine-structured lithium metal oxides
• the electronic conductivity of the metal oxide compounds which can be used according to the invention at room temperature is at least 10 7 S / cm, preferably at least 10 6 S / cm and particularly preferably at least 10 5 S / cm.
• the rechargeable high-energy battery according to the invention has a negative electrode (anode) which contains a material with an electrochemical potential ⁇ 2 V against Li / Li + .
• a negative electrode anode
• M 2 an alkaline earth element (Mg, Ca, Sr, Ba or any mixture thereof) and
• the metal nitrogen compounds correspond to the general formulas (III) and / or (IV)
• Metal nitrogen compounds are preferably used as electrochemically active anode materials, the metal nitrogen compounds being embedded in a transition-metal-containing electronic or mixed-conductive network.
• the electrochemically active metal nitrogen compound In the fully discharged (low-lithium) state of charge, the electrochemically active metal nitrogen compound has a composition which is indicated by at least one of the two general formulas (I) and / or (II).
• the transition metal-containing electronic or mixed-conductive network contains finely divided transition metals M in elemental form or finely divided conductive interstitial transition metal compounds with an electrochemical potential (lithium intercalation potential) of ⁇ 2.5 V against Li / Li + .
• Transition metal compounds with an electrochemical potential (lithium intercalation potential) of ⁇ 2.5 V against Li / Li + .
• Both binary (MN X , MC X, MH X ) and ternary (MM ' y N x ; MM'yC x ; MM' y H x ) and higher mixed phases can be used, the further metal M 'being at least one further transition metal from the 3rd to 12th group of the periodic table (M x M ' y N z ) and / or the element is lithium (Li y MN x ; Li y MC x ; LiwM x M' y N z ; Li w M x M'yH z ; etc).
• the nitridometalates preferably consist of at least one of the following compounds: Li 2 NH, MgNH, CaNH, Li 2 Mg (NH) 2, Li 2 Ca (NH) 2, MgCa ( NH) 2, Li 4 Mg (NH) 3, Li 2 Mg 2 (NH) 3 and / or according to the generic formula (II) from one or more of the following compounds: LiNH 2 , Mg (NH 2 ) 2 , Ca ( NH 2 ) 2 .
• the active N-containing anode materials change into a lithium-rich state.
• the lithium-rich compounds are formed according to the generic formulas (III), preferably: Li 4 NH, Li 2 MgNH, Li 2 CaNH, Li 6 Mg (NH) 2, Li 6 Ca (NH) 2 , Li 4 MgCa (NH ) 2, Lii 0 Mg (NH) 3, Li 8 Mg 2 (NH) 3 and / or according to the generic formula (IV), preferably: Li 3 N, MgLiN, CaLiN and LiH.
• the stoichiometries given indicate the highest or highest levels (limit stoichiometries) of carbon, nitrogen or hydrogen.
• interstitial compounds are not exactly stoichiometric compounds, that is to say all compositions, starting from the pure metal to the limit stoichiometry, are generally possible and mostly stable. All compounds with lower foreign element contents, i.e. qualitatively represented by Li w M x M ' y E z-6 (5 can have any value between 0 and z), are also electronic or mixed-conducting materials and are therefore suitable for the division of the nitrogen-containing composite anode materials .
• the electronically conductive transition metals or their corresponding likewise electronically conductive nitride, carbide or hydride compounds are preferably used in finely divided form (nanoparticulate). They can be mixed as homogeneously as possible with the anode material, which also contains nanoparticulate lithium nitrogen, using a physical mixing process, with subsequent pressing (in technical manufacturing processes generally by calendering) in the anode strip production ensuring good contacting of the individual particles and the fully functional nitrogen and transition metal containing composite anode material is obtained. Suitable composite anode materials can also be produced by chemical processes, for example reactions with nitrogen sources.
• Elemental nitrogen (N 2 ) serves as the preferred nitrogen source; Ammonia (NH3); Hydrazine (N 2 H 4 ); Urea (CH 4 N 2 0).
• the metals that is to say lithium and the selected transition metals, are reacted with ammonia, preferably at elevated temperatures and under pressure conditions.
• the amide compounds obtained can then be converted further by subsequent thermolysis, for example into imide compounds and / or nitrides.
• appropriate transition metal hydrides and / or transition metal carbides can be added before or after ammonolysis. After removing excess ammonia, the remaining solids can be ground together. This measure causes a particle size reduction and an improvement in the contact.
• nitridic phases form immediately. In this case, too, desired non-non-iridic conductivity improvers can be added.
• the lithium nitrogen-containing anode materials are co-ground with the conductivity-improving transition metals or their nitrides, carbides or hydrides.
• a high-energy mill for example of the planetary ball mill type, is used for the grinding.
• Non-metal-based conductivity improvers primarily include non-metal-based conductivity improvers, lithium-donating additives and binders. All conductive forms of elemental carbon (graphite, carbon black, graphene, carbon nanotubes) come into consideration as non-metal-based conductivity improvers.
• Lithium-metal additives preferably coated, ie surface passivated and in powder form or as a thin film
• the organic polymers conventionally used for the production of electrodes can be used as binders. These include PTFE, PVdF, polyisobutylene (eg: Oppanols ® from BASF) and similar materials.
• the ready-to-use (complete) nitrogen and transition metal-containing composite anode can also contain further conductivity improvers (up to 30% by weight), binders (up to 20% by weight) and / or prelithiating agents (up to 20% by weight).
• Anodes containing metallic lithium are also preferably used, where the lithium is present either as a sheet metal or powder electrode or as an alloy with a metal selected from silicon, tin, boron and aluminum.
• the composite cathode which is in the State before the first discharge in an electronically or mixed-conductive network embedded lithium hydroxide and, if necessary, additionally contains one or more lithium oxygen compounds selected from L12O, L12O2 and L1O2, come the types familiar to the person skilled in the art (liquid, gel, polymer and Solid electrolytes) in question.
• soluble lithium salts with weakly coordinating, oxidation-stable anions are used as the conductive salt for liquid, polymer and gel-polymer systems.
• LiPF 6 lithium fluoroalkylphosphates
• LiBF 4 imide salts (e.g. LiN (S0 2 CF3) 2), UOSO2CF3, methide salts (e.g. LiC (S0 2 CF 3 ) 3), LiCI0 4 , lithium chelatoborates (e.g. LiB (C20 4 ) 2 , also called “LiBOB”), lithium fluorochelatoborates (e.g. LiC 2 0 4 BF 2 , called “LiDFOB”), lithium chelatophosphates (e.g. LiP (C 2 0 4 ) 3 , called “LiTOP”) and
• Lithium fluorochelatophosphates e.g. Li (C 2 0 4 ) 2 PF 2 . Salts with anions which are stable against anion dissociation and which are fluorine-free are particularly preferred.
• Solid electrolytes ie Li-ion-conducting glasses, ceramics or crystalline inorganic solids are also particularly preferred.
• Borohydride compounds e.g. LiBH 4 , and L12B12H12.
• the anode compartment is separated from the cathode compartment by means of a lithium ion-permeable but electronically insulating separator (e.g. consisting of microporous polyolefins) or a solid electrolyte (of the type of an inorganic solid or a solid polymer material).
• a lithium ion-permeable but electronically insulating separator e.g. consisting of microporous polyolefins
• a solid electrolyte of the type of an inorganic solid or a solid polymer material
• the grinding bowl was reinserted into the Ar-filled Flandschuh box and opened there.
• the ground product was separated from the grinding media by sieving.
• the filter residue was first predried in vacuo and then sintered for 5 hours at 300 ° C. in an oxygen atmosphere.
• the powder contains 15% Co 3 0 4 and about 73% LiOH; the rest at 100% consists essentially of lithium oxide.

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• 2019
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