EP0948826A1 - Method and anode for improving the power density of lithium secondary batteries - Google Patents

Method and anode for improving the power density of lithium secondary batteries

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Publication number
EP0948826A1
EP0948826A1 EP97953650A EP97953650A EP0948826A1 EP 0948826 A1 EP0948826 A1 EP 0948826A1 EP 97953650 A EP97953650 A EP 97953650A EP 97953650 A EP97953650 A EP 97953650A EP 0948826 A1 EP0948826 A1 EP 0948826A1
Authority
EP
European Patent Office
Prior art keywords
boric acid
anode
additives
lithium
compounds
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP97953650A
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German (de)
French (fr)
Inventor
Franz W. Winterberg
Bent Hundrup
Dennis W. Nielsen
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Individual
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Individual
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Publication date
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Publication of EP0948826A1 publication Critical patent/EP0948826A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/04—Esters of boric acids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/18—Cells with non-aqueous electrolyte with solid electrolyte
    • H01M6/181—Cells with non-aqueous electrolyte with solid electrolyte with polymeric electrolytes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention relates to methods and anodes for improving the power density of lithium secondary batteries, in particular those with solid polymer solutions.
  • the current density of the electrolytes is expressed as:
  • L E is the conductivity of the electrolyte solution
  • ⁇ ⁇ is the potential difference between the anode and cathode material
  • tj r is the reduced transport size of the transport species “i”
  • ⁇ ⁇ i is the difference in the chemical potential of the species “i” between the anodes - and cathode material.
  • boric acid esters and / or boric acid ester derivatives or their compounds are added as additives to improve the power density of lithium secondary batteries, in particular those with solid polymer solutions
  • boric acid esters and / or boric acid ester derivatives are used as lithium compounds in complexes of the formula
  • R 1 and R 2 can be aromatic and / or aliphatic and in formula III M is a transition metal and the cyclopetadienyl groups can also carry fluorine instead of H.
  • Transition metals are elements whose atoms have an incomplete d-shell or which can form one or more cations with incomplete d-shells 21 - 30 in the 5th period Y to Cd (39-48), in the 6th period La to Hg including the lanthanoids, in which the 4f shell is filled (atomic numbers 57-80) and in the 7th period Ac, the actinides to Lr (89-103) Boric acid esters are preferably used
  • the residual groups cause electrochemical stability and solubility in the organic solvent. Due to the large and voluminous residual groups, the negative charge is distributed. As a result, it is very unlikely that lithium + will form ion pairs or complex species.
  • the salt is therefore dissolved or dissolved in the organic solvent dissociates
  • the additives are preferably added on the anode side
  • the additives are added in amounts of> 0 to 20% by weight, preferably 5 to 15% by weight
  • the anode according to the invention in particular in lithium ion secondary batteries and those with solid polymer solutions, contains additions of boric acid esters and / or boric acid ester derivatives or their compounds at the anode
  • the anode consists of a substance that can store lithium ions and / or lithium and conductive salts that are dissolved in solvents and / or in polymer binders and / or a conductive carbon black and / or the additive.
  • Such anodes are particularly suitable, the lithiated boric acid ester and / or boric acid ester derivatives in the form of complex compounds of the formulas
  • the additives are expediently contained in the anodes in amounts of greater than 0 to 20% by weight, preferably 5 to 15% by weight
  • Figure 1 is a schematic sectional view of a battery, for example a lithium ion battery LiC / PEO, lithium salt / Li Mn 2 0 $ without salt, with very low electrical currents in a very short time (idealized case)
  • Figure 2 is a schematic sectional view of the same system, in the difference for Figure 1, the graphs show the behavior when using larger currents
  • FIG. 3 is again a schematic sectional view of the same system, the graphs show the behavior with small and large currents, there is no salt emptying
  • FIG. 4 trends in the curve representations for small, medium and large currents
  • FIG. 5 curve representation as in FIG. 4, but ideally with immobilized anions
  • FIG. 6 shows schematic exemplary representations of how the cycle strength can be increased on the basis of the use case of polyethylene oxide (PEO)
  • FIG. 7 shows the positive derivation of 1 Ohm's law achieved using the additive substances in comparison to the curve profile without positive derivation
  • Figure 8 is a schematic representation of anodes / electrolyte / cathodes for the application of the additives and without their use
  • FIG. 2 shows the conditions for larger currents in the same system of a lithium ion battery used as an example, local drainage of the seeds occurs. Due to the existence of a mass balance of the lithium ions, their concentration is approximately constant (A)
  • the anions move towards the electrolyte against the positive electrode. Since no anions are supplied from the electrodes, a concentration gradient is created (B) According to Kohlrausch's law, the ion conductivity depends on the electrolyte concentration. If the concentration decreases, the conductivity also decreases If a concentration gradient occurs, a gradient of the conductivity arises (C) If the electrolyte conductivity decreases, the local electrolyte resistance increases With an increase in the local electrolyte resistance, a potential drop occurs (D)
  • the ideal case shown in FIG. 5 with immobilized anions will be explained in more detail below by way of example.
  • the anions are not mechanically immobilized, but their transport size is very small in relation to lithium If the anions are mechanically immobilized, the complex constant is very large, the order of magnitude of the lithium transport decreases. The overall conductivity decreases because the complex constant between the anions and lithium is large
  • FIG. 6 is based on the state that if a larger current is required, a high potential must be used. High potentials give only small numbers of cycles or only a limited cycle stability. This is shown in FIG. 6 using the example of the PEO solvent
  • FIG. 6 shows the achievement of retained currents according to the invention with then reduced potentials which are of the order of magnitude where the PEO solvent is stable.
  • the cycle ability could be increased by using the substances according to the invention above the reduced potentials thus achieved but the constant current achieved.
  • the reduced potential increases the number of cycles or the cycle strength
  • the invention achieved particularly advantageously that when the substances according to the invention were added to the electrolyte binder material in the anode, the potential, as exemplified in FIG. 6, could be reduced, without reducing the current density
  • FIG. 7 shows schematically the so-called positive derivatives of First Ohm's law achieved in addition to the graph of the normal course of First Ohm's law for ordinary batteries in lithium ion battery systems described
  • the potential for the investigations was determined to be constant.
  • the additive complexes or the substances found were added, and a positive derivation of the first Ohm's law was found.This means a larger current compared to the normally achievable course according to the first Ohm's law
  • the measurements were carried out in a lithium half-cell with an active area of approximately 1 cm 2 (standard electrolyte LP 30 EC DMC (1 1), 1 m L ⁇ PF 6 , feed rate 0.1 mV / s)

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to a method and anode for improving power density of lithium secondary batteries, specially those containing solid polymer solutions. This is done by employing boric acid esters and/or boric acid derivatives or the compounds thereof as additives. Lithium compounds in corresponding complexes are specially added. The invention also includes anodes for use in galvanic cells, specially in lithium ion secondary batteries and those with solid polymer solutions, which contain boric acid esters and/or boric aid ester derivatives or the compounds thereof as additives in the anode.

Description

Verfahren und Anode zur Verbesserung der Leistungsdichte von LithiumsekundärbatterienMethod and anode for improving the power density of lithium secondary batteries
Die Erfindung betrifft Verfahren und Anode zur Verbesserung der Leistungsdichte von Lithiumsekundärbatterien, insbesondere solchen mit festen Polymerlösungen.The invention relates to methods and anodes for improving the power density of lithium secondary batteries, in particular those with solid polymer solutions.
In Zellanordnungen und weiteren Anordnungen wird eine verbesserte Materialausnutzung gewünscht, um die Anforderungen der Nachfrager befriedigen zu können. Wenn die Ladung von Anoden zum Kathodenmaterial vorrangig in einer sekundären Batterie durch einen Elektrolyten bzw. durch eine Elektrolytlösung transportiert wird, so ist das darauf zurückzuführen, daß jedwede Materialien mit einem Potential transportiert werden. Folglich werden die positiv geladenen Ionen auch durch die Elektrolyte zur negativ geladenen Elektrode transportiert. Umgekehrt gilt dies für die Anionen.Improved material utilization is desired in cell arrangements and other arrangements in order to be able to satisfy the demands of the customers. If the charge from anodes to the cathode material is primarily transported in a secondary battery by an electrolyte or by an electrolyte solution, this is due to the fact that any materials with a potential are transported. As a result, the positively charged ions are also transported through the electrolytes to the negatively charged electrode. Conversely, this applies to the anions.
Die Stromdichte der Elektrolyte wird ausgedrückt als:The current density of the electrolytes is expressed as:
wobei LE die Konduktivität der Elektrolytlösung ist, Δ φ ist die Potentialdifferenz zwischen dem Anoden- und Kathodenmaterial, tjr ist die reduzierte Transportgröße der Transportspezies „i", und Δ μi ist die Differenz des chemischen Potentials der Spezie „i" zwischen dem Anoden- und Kathodenmaterial.where L E is the conductivity of the electrolyte solution, Δ φ is the potential difference between the anode and cathode material, tj r is the reduced transport size of the transport species “i”, and Δ μi is the difference in the chemical potential of the species “i” between the anodes - and cathode material.
Da alle Materialien in der Anode definiert verdünnt sind, ist dann Δ μ,- ungefähr 0, für gewöhnliche Batterien, wie beispielhaft (1) erläutert, wird dann ein Äquivalent des ersten Ohmschen Gesetzes eintreten.Since all materials in the anode are defined and diluted, Δ μ is approximately 0, for ordinary batteries, as explained by way of example (1), an equivalent of the first Ohm's law will then occur.
Es können höhere Spannungen auftreten, als für das System vorgesehen ist. Dieses kann zu Risiken und Schäden führen, die präventiv zu vermeiden sind. Schließlich ist die Bindung der Polymere unvorteilhaft, die Aπioπen sind nicht immobilisiert Die Transportgroßenordπung des Lithiums ist unbefriedigendHigher voltages can occur than the system is designed for. This can lead to risks and damage that must be avoided preventively. Finally, the binding of the polymers is disadvantageous, the anion is not immobilized. The transport order size of the lithium is unsatisfactory
Somit besteht die Aufgabe der vorliegenden Erfindung dann, vorrangig für Lithium- sekundarbattenen einen Zusatz bereitzustellen, der die Leistungsdichte unter Berücksichtigung der Betriebssicherheit erhöht, eine positive Abweichung des ersten Ohmschen Gesetzes erreicht, die Salzausleerung vermindert und die Zykleπaπzahl bzw Zyklenfestigkeit erhöht Ferner waren Verfahrensschritte zu erarbeiten, die die angeführten Verbesserungen erbringenIt is therefore the object of the present invention to provide an additive primarily for lithium secondary batteries which increases the power density while taking operational safety into account, achieves a positive deviation from Ohm's first law, reduces salt emptying and increases the number of cycles or cycle strength. Process steps also had to be worked out who bring the improvements mentioned
Die Aufgabe wird durch die kennzeichnenden Merkmale gemäß der Patentansprüche gelost Demgemäß werden zur Verbesserung der Leistungsdichte von Lithiumsekun- darbatteπen insbesondere solchen mit festen Polymerlosungen Borsaureester und/oder Borsaureesterdenvaten oder deren Verbindungen als Additive zugesetztThe object is achieved by the characterizing features according to the claims. Accordingly, boric acid esters and / or boric acid ester derivatives or their compounds are added as additives to improve the power density of lithium secondary batteries, in particular those with solid polymer solutions
Der Zusatz bewirkt daß die sogenannte Salzausleerung (Fig 3) vermindert wird, eine hohe Lithiumtransportgroßenordnung erreicht wird sowie eine positive Deπ- vation des 1 Ohmschen Gesetzes (Fig 4) resultiert Dies bewirkt auch eine erhöhte Zyklenfestigkeit des Batteriesystems sowie für festgelegte Potentiale eine Erhöhung der Leistungsdichte Das verwendete Zellsystem geht aus den Figuren hervorThe addition causes the so-called salt emptying (FIG. 3) to be reduced, a high order of lithium transport is achieved and a positive deviation of the 1 Ohm law (FIG. 4) results The cell system used is shown in the figures
Insbesondere werden Borsaureester und/oder Borsaureesterdeπvate als Lithium- verbindungen in Komplexen der FormelIn particular, boric acid esters and / or boric acid ester derivatives are used as lithium compounds in complexes of the formula
und/oder and or
π und/oder π and / or
verwendet wobei die Restgruppen Ri und R2 aromatisch und/oder aliphatisch sein können und in Formel III M ein Ubergangsmetall ist und die Cyclopeπtadienyl- Gruppen auch Fluor anstelle von H tragen könnenused wherein the residual groups R 1 and R 2 can be aromatic and / or aliphatic and in formula III M is a transition metal and the cyclopetadienyl groups can also carry fluorine instead of H.
Ubergangsmetalle sind solche Elemente, deren Atome eine inkomplette d-Schale haben oder die ein oder mehrere Kationen mit inkompletten d-Schalen bilden können Demnach gehören gemäß der von der IUPAC empfohlenen Notation zu den Ubergangsmetalleπ in der 4 Periode die Elemente Sc bis Zn mit den Ordnungszahlen 21 - 30 in der 5 Periode Y bis Cd (39-48), in der 6 Periode La bis Hg einschließlich der Lanthanoide, bei denen die 4f-Schale aufgefüllt wird (Ordnungszahlen 57-80) und in der 7 Periode Ac, die Actinoide bis Lr (89-103) Vorzugsweise werden Borsaureester verwendetTransition metals are elements whose atoms have an incomplete d-shell or which can form one or more cations with incomplete d-shells 21 - 30 in the 5th period Y to Cd (39-48), in the 6th period La to Hg including the lanthanoids, in which the 4f shell is filled (atomic numbers 57-80) and in the 7th period Ac, the actinides to Lr (89-103) Boric acid esters are preferably used
Die Restgruppen bedingen elektrochemische Stabilität und Los chkeit im organischen Losungsmittel Durch die großen und voluminösen Restgruppen ist die negative Ladung verteilt Dies hat zur Folge, daß es sehr unwahrscheinlich ist, daß Lιthιum+ lonenpaare oder komplexierte Spezies bildet Daher ist das Salz im organischen Losungsmittel gelost bzw dissoziiertThe residual groups cause electrochemical stability and solubility in the organic solvent. Due to the large and voluminous residual groups, the negative charge is distributed. As a result, it is very unlikely that lithium + will form ion pairs or complex species. The salt is therefore dissolved or dissolved in the organic solvent dissociates
Vorzugsweise werden die Additive an der Anodenseite zugesetztThe additives are preferably added on the anode side
Die Additive werden in Mengen von > 0 bis 20 Gew %, vorzugsweise 5 bis 15 Gew % zugegebenThe additives are added in amounts of> 0 to 20% by weight, preferably 5 to 15% by weight
Die erfindungsgemaße Anode, insbesondere in Lithiumionensekundarbatteπen und solchen mit festen Polymerlosungen, enthalt an der Anode Zusätze von Borsaureester und/oder Borsaureesterdeπvaten oder deren VerbindungenThe anode according to the invention, in particular in lithium ion secondary batteries and those with solid polymer solutions, contains additions of boric acid esters and / or boric acid ester derivatives or their compounds at the anode
Damit wird ein vergleichsweise hoher Strom bei niedrig gewähltem Potential mit insbesondere den Effekten eines stabilen Systems sowie höhere Zyklenzahl bzw Zyklenfestigkeit erreichtThis achieves a comparatively high current with a low potential, in particular with the effects of a stable system and a higher number of cycles or cycle stability
Die Anode besteht aus einer Substanz, die Lithiumionen einlagern kann und/oder Lithium und Leitsalzen, die in Losungsmitteln gelost sind und/oder in Polymerbinde- mittel und/oder einem Leitruß und/oder dem Additiv Besonders geeignet sind solche Anoden die lithnerte Borsaureester und/oder Borsaureesterdeπvate in Form komplexer Verbindungen der Formeln The anode consists of a substance that can store lithium ions and / or lithium and conductive salts that are dissolved in solvents and / or in polymer binders and / or a conductive carbon black and / or the additive. Such anodes are particularly suitable, the lithiated boric acid ester and / or boric acid ester derivatives in the form of complex compounds of the formulas
und/oderand or
π π
und/oderand or
als Zusatz enthalten. Die Zusätze sind zweckmäßig in Mengen von großer als 0 bis 20 Gew %, vorzugsweise 5 bis 15 Gew %, in den Anoden enthaltenincluded as an additive. The additives are expediently contained in the anodes in amounts of greater than 0 to 20% by weight, preferably 5 to 15% by weight
Die Erfindung sei im folgenden naher unter Bezugnahme auf die beigefugten Zeichnungen erläutert In den Zeichnungen zeigenThe invention is explained in more detail below with reference to the accompanying drawings, in which:
Figur 1 eine schematische Schnittdarstellung einer Batterie, beispielhaft eine Lithiumionenbatterie LiC/PEO, Lithiumsalz/Li Mn20$ ohne Salzausieerung, mit sehr geringen elektrischen Strömen in sehr kurzer Zeit (idealisierter Fall), Figur 2 eine schematische Schnittdarstellung des gleichen Systems, im Unterschied zu Figur 1 zeigen die Kurvendarstellungen hier das Verhalten bei Nutzung größerer StromeFigure 1 is a schematic sectional view of a battery, for example a lithium ion battery LiC / PEO, lithium salt / Li Mn 2 0 $ without salt, with very low electrical currents in a very short time (idealized case), Figure 2 is a schematic sectional view of the same system, in the difference for Figure 1, the graphs show the behavior when using larger currents
Figur 3 wiederum eine schematische Schnittdarstellung des gleichen Systems, die Graphen zeigen das Verhalten bei kleinen und großen Strömen, es tritt keine Salzentleerung aufFigure 3 is again a schematic sectional view of the same system, the graphs show the behavior with small and large currents, there is no salt emptying
Figur 4 Tendenzen in den Kurvendarstellungen für kleinere, mittlere und größere Strome,FIG. 4 trends in the curve representations for small, medium and large currents,
Figur 5 Kurvendarstellung wie in Figur 4 jedoch im Idealfall mit immobilisierten Anionen,FIG. 5 curve representation as in FIG. 4, but ideally with immobilized anions,
Figur 6 schematische beispielhafte Kurvendarstellungen, wie die Zyklenfestigkeit erhöht werden kann anhand des Einsatzfalles Polyethyleπoxid (PEO), Figur 7 Kurvendarstelluπg der unter Einsatz der Additivstoffe erreichten positiven Derivation des 1 Ohmschen Gesetzes im Vergleich zum Kurvenverlauf ohne positive DerivationFIG. 6 shows schematic exemplary representations of how the cycle strength can be increased on the basis of the use case of polyethylene oxide (PEO), FIG. 7 shows the positive derivation of 1 Ohm's law achieved using the additive substances in comparison to the curve profile without positive derivation
Figur 8 eine schematische Darstellung Anoden/Elektrolyt/Kathoden für den Einsatzfall der Additivstoffe und ohne deren EinsatzFigure 8 is a schematic representation of anodes / electrolyte / cathodes for the application of the additives and without their use
Figur 9 Strom-Spannungs-Diagramm zur Darstellung der Ergebnisse in den BeispielenFigure 9 Current-voltage diagram to illustrate the results in the examples
In Anordnungen wie schematisch beispielsweise in Figur 1 dargestellt, treten in Fallen sehr geringer Strome in kurzen Zeitimpulsen keine Salzentleerungen auf Das gilt insbesondere für die skizzierten Lithiumionenbatterien dargestellt gemäß Figur 1 im Idealfall, die Anionen sind nicht immobilisiert Deshalb können nur geringe Strome in kurzer Zeit ohne Gradienten entnommen werdenIn arrangements as shown schematically, for example in FIG. 1, in the case of very low currents, no salt evacuation occurs in short time pulses. This applies in particular to the lithium ion batteries shown in FIG. 1 ideally, the anions are not immobilized. Therefore, only small currents can be drawn in a short time without gradients
Die Figur 2 gibt die Verhaltnisse bei größeren Strömen im gleichen beispielhaft verwendeten System einer Lithiumionenbatterie wieder, es treten lokale Saizentleerun- gen auf Aufgrund der Existenz einer Massenbalance der Lithiumionen ist deren Konzentration naherungsweise konstant (A)FIG. 2 shows the conditions for larger currents in the same system of a lithium ion battery used as an example, local drainage of the seeds occurs. Due to the existence of a mass balance of the lithium ions, their concentration is approximately constant (A)
Die Anionen bewegen sich zum Elektrolyten gegen die positive Elektrode Da keine Anionen von den Elektroden nachgeliefert werden, entsteht ein Konzentrationsgra- dient (B) Entsprechend dem Gesetz von Kohlrausch hangt die lonenleitfahigkeit von der Elektrolytkonzeπtration ab Wenn die Konzentration abnimmt, nimmt auch die Leitfähigkeit ab Ferner entsteht mit dem Auftreten eines Konzentrationsgradienten ein Gradient der Leitfähigkeit (C) Wenn die Elektrolytleitfahigkeit abnimmt nimmt der lokale Elektrolytwiderstand zu Mit einem Zuwachs des lokalen Elektrolytwiderstands tritt ein Potentialabfall auf (D)The anions move towards the electrolyte against the positive electrode. Since no anions are supplied from the electrodes, a concentration gradient is created (B) According to Kohlrausch's law, the ion conductivity depends on the electrolyte concentration. If the concentration decreases, the conductivity also decreases If a concentration gradient occurs, a gradient of the conductivity arises (C) If the electrolyte conductivity decreases, the local electrolyte resistance increases With an increase in the local electrolyte resistance, a potential drop occurs (D)
Gemäß Figur 3 sind die Anionen nunmehr erfindungsgemaß in der Polymermatrix des Elektrolyten immobilisiertAccording to FIG. 3, the anions are now immobilized according to the invention in the polymer matrix of the electrolyte
So sind große und kleine Strome, ohne dann Probleme mit der Salzausieerung zu haben und damit Potentialabfalle zu verzeichnen, nutzbar, wie ebenso Figur 5 als Tendenz in den Kurvendarstellungen im Idealfall mit immobilisierten Anionen zeigtIn this way, large and small currents can be used without having problems with salt precipitation and thus registering potential drops, as is also shown in FIG. 5 as a trend in the graphs in the ideal case with immobilized anions
Für kleinere, mittlere und größere Strome sind die beschriebenen Tendenzen in den Kurvendarstellungen der Figur 4 zusammengefaßtThe tendencies described for smaller, medium and larger currents are summarized in the graphs in FIG
Der gemäß Figur 5 gezeigte Idealfall mit immobilisierten Anionen soll nachstehend beispielhaft naher erläutert werden Die Anionen sind nicht mechanisch immobilisiert sondern ihre Transportgroßenordnuπg ist im Verhältnis zum Lithium sehr klein Wenn die Anionen mechanisch immobilisiert sind, dann ist die Komplexkonstante sehr groß, die Lithiumtransportgroßenordnung fallt ab Die Gesamtkonduktivitat fallt ab, da die Komplexkonstante zwischen Anionen und Lithium groß istThe ideal case shown in FIG. 5 with immobilized anions will be explained in more detail below by way of example. The anions are not mechanically immobilized, but their transport size is very small in relation to lithium If the anions are mechanically immobilized, the complex constant is very large, the order of magnitude of the lithium transport decreases. The overall conductivity decreases because the complex constant between the anions and lithium is large
Wenn die Anionen chemisch immobilisiert sind, dann ist die Komplexkonstante zwischen Lι+ und Anion sehr hoch, die Gesamtkonduktivitat ist sehr niedrig Wenn jedoch der Anionentransport im Vergleich zur Lι+ -Transportgroßenordπung sehr klein ist dann existieren keine signifikanten Komplexe zwischen den Anionen und Kationen Somit ergibt sich eine hohe KonduktivitatIf the anions are chemically immobilized, the complex constant between Lι + and anion is very high, the overall conductivity is very low. However, if the anion transport is very small compared to the Lι + transport order, there are no significant complexes between the anions and cations high conductivity
Figur 6 basiert auf dem Stand, daß, wenn man einen größeren Strom benotigt, man ein hohes Potential nutzen muß Hohe Potentiale geben nur geringe Zyklenzahlen bzw nur eine bedingte Zyklenfestigkeit Dies wird in Figur 6 am Beispiels des PEO- Solvents gezeigtFIG. 6 is based on the state that if a larger current is required, a high potential must be used. High potentials give only small numbers of cycles or only a limited cycle stability. This is shown in FIG. 6 using the example of the PEO solvent
Weitergehend zeigt Figur 6 die erfindungsgemaße Erreichung beibehaltener Strome bei dann verminderten Potentialen, die sich in den Größenordnungen befinden, wo das PEO-Solvent stabil ist Die Zyklenfahigkeit konnte bei Verwendung der erfindungsgemaßen Stoffe über somit erreichte verminderte Potentiale aber erreichten gleichbleibenden Strom erhöht werden Das verminderte Potential erhöht die Zyklenzahl bzw die Zyklenfestigkeit Im beispielhaft gemäß Figur 1 zugrundegelegten System einer Lithiumionenbattene wurde erfindungsgemaß besonders vorteilhaft erreicht, daß bei Zugabe der erfindungsgemaßen Stoffe gemäß der Patentansprüche zum Elektrolytbindermateπal in der Anode, das Potential, wie in Figur 6 beispielhaft gezeichnet, reduziert werden konnte, ohne die Stromdichte zu reduzierenFurthermore, FIG. 6 shows the achievement of retained currents according to the invention with then reduced potentials which are of the order of magnitude where the PEO solvent is stable. The cycle ability could be increased by using the substances according to the invention above the reduced potentials thus achieved but the constant current achieved. The reduced potential increases the number of cycles or the cycle strength In the system of a lithium ion battery used as an example in FIG. 1, the invention achieved particularly advantageously that when the substances according to the invention were added to the electrolyte binder material in the anode, the potential, as exemplified in FIG. 6, could be reduced, without reducing the current density
In Versuchsreihen konnte die Leistungsdichte des Systems erhöht und der Nacnweis hierzu gefuhrt werden So zeigt Figur 7 schematisch die erreichte sog Positive Derivationen des Ersten Ohmschen Gesetzes neben dem Graphen des normalen Verlaufs des Ersten Ohmschen Gesetzes für ordinäre Batterien in beschriebenen Lithiumionenbatteπesystemen Für die Untersuchungen wurde das Potential gleichbleibend festgelegt Die Additivkomplexe bzw die gefundenen Stoffe wurden zugesetzt, und eine positive Derivation des Ersten Ohmschen Gesetzes wurde festgestellt Das bedeutet einen größeren Strom verglichen mit dem normal erreichbaren Verlauf gemäß dem Ersten Ohmschen Gesetz Somit ist die Leistungsdichte des Systems erhöhtIn series of tests, the power density of the system could be increased and the reference made to it. For example, FIG. 7 shows schematically the so-called positive derivatives of First Ohm's law achieved in addition to the graph of the normal course of First Ohm's law for ordinary batteries in lithium ion battery systems described The potential for the investigations was determined to be constant. The additive complexes or the substances found were added, and a positive derivation of the first Ohm's law was found.This means a larger current compared to the normally achievable course according to the first Ohm's law
Aus der unter Figur 8 aufgeführten Gleichung sowie aus der Zeichnung ergibt sich, daß die Transportgroßenordnung der Anionen ungefähr 0 ist. Somit beeinflußt die chemische Potentialdifferenz die Stromdichte in keiner Weise Wenn ein lithiertes Borsaureesterdenvat hinzugefugt wurde, wird die partiale Uber- schußenergie der Lithiumionen bestandig positiv Das basiert auf einer erhöhten Stromdichte sowie einer erhöhten Lithiumtransportgroßenordnung Dann istIt can be seen from the equation shown in FIG. 8 and from the drawing that the transport order of the anions is approximately 0. Thus, the chemical potential difference does not influence the current density in any way. If a lithiated boric acid ester derivative is added, the partial excess energy of the lithium ions becomes consistently positive. This is based on an increased current density and an increased order of magnitude of lithium transport
dj_ _ 0 und RT d In Xu o dx dxdj_ _ 0 and RT d In X uo dx dx
und t,r Δ μ, » ... > 0 volt (2).and t, r Δ μ, »...> 0 volt (2).
Damit ist eine positive Derivation des Ersten Ohmschen Gesetzes gegebenThis provides a positive derivation of Ohm's First Law
Für festgelegte Zelldesigne und Potentiale kann ein größerer Strom in einen äußeren Stromkreis entnommen werden, wenn das System positiv vom Ersten Ohmschen Gesetz abweicht Dies bedeutet somit eine erhöhte Leistungsdichte Beispiel 1 (Vergleichsbeispiel)For defined cell designs and potentials, a larger current can be drawn into an external circuit if the system deviates positively from First Ohm's Law. This means an increased power density Example 1 (comparative example)
Rezepturen ohne Lιthιum-bιs[1 ,2-benzoldιolato(2-)-0,0']borat(1-)(LιBSE)Recipes without Lιthιum-bιs [1, 2-benzoldιolato (2 -) - 0.0 '] borate (1 -) (LιBSE)
Aktivmaterial GewichtsprozentActive material weight percent
Graphit (Typ KS6) 90,29Graphite (type KS6) 90.29
Leitruß (Typ Super P) 4,74Guide carbon black (type Super P) 4.74
Teflon-Binder 4,97Teflon binder 4.97
(Gesamtmasse der Elektrode 13,9 mg Aktivmasse an kS6 12,55 mg, äquivalent mit(Total mass of the electrode 13.9 mg active mass of kS6 12.55 mg, equivalent to
4 67 mAh)4 67 mAh)
Beispiel 2Example 2
Rezeptur mit Lιthιum-bιs[1 ,2-benzoldιolator(2-)-0,0']borat(1 -)(LιBSE)Recipe with Lιthιum-bιs [1, 2-benzeneιolator (2 -) - 0.0 '] borate (1 -) (LιBSE)
Aktivmaterial GewichtsprozentActive material weight percent
Graphit (Typ KS 6) 82,08Graphite (type KS 6) 82.08
Leitruß (Typ Super P) 4,30Carbon black (type Super P) 4.30
Teflon-Binder 4,53Teflon binder 4.53
LiBSE 9,09LiBSE 9.09
(Gesamtmasse der Elektrode 1 1 3 mg, Aktivmasse an KS6 9,3 mg äquivalent mit 3 46 mAh)(Total mass of the electrode 1 1 3 mg, active mass at KS6 9.3 mg equivalent to 3 46 mAh)
In beiden Beispielen erfolgten die Messungen in einer Lithium-Halbzelle mit einer Aktivfiache von ca 1 cm2 (Standardelektrolyt LP 30 EC DMC (1 1 ), 1 m LιPF6, Vorschubgeschwindigkeit 0,1 mV/s)In both examples, the measurements were carried out in a lithium half-cell with an active area of approximately 1 cm 2 (standard electrolyte LP 30 EC DMC (1 1), 1 m LιPF 6 , feed rate 0.1 mV / s)
Zur Darstellung der Elektroden wurden die entsprechenden Aktivmaterialien in einem Morser vermischt und auf das Nickelnetz gepreßt Ein Cydovoltamogramm wurde mit diesen zwei Zusammensetzungen an einem ansteuerbaren Potentiostaten erstellt, wie es in Figur 9 (Strom-Spannungsdiagramm) zu sehen ist. Aus dieser Figur 9 ergibt sich, daß der Kathoden und Anodenstrom erhöht ist. Daraus folgt, daß die Kapazität im System mit LiBSE (Beispiel 2) im Vergleich zum System ohne LiBSE (Beispiel 1 ) erhöht ist. To display the electrodes, the corresponding active materials were mixed in a Morser and pressed onto the nickel mesh A cydovoltamogram was created with these two compositions on a controllable potentiostat, as can be seen in FIG. 9 (current-voltage diagram). From this Figure 9 it follows that the cathode and anode current is increased. It follows that the capacity in the system with LiBSE (example 2) is increased compared to the system without LiBSE (example 1).

Claims

Patentansprüche claims
1 Verfahren und Anode zur Verbesserung der Leistungsdichte von Lithium-1 Method and anode to improve the power density of lithium
Sekundärbatteπen, insbesondere solchen mit festen Polymerlösungen, dadurch gekennzeichnet, daß Borsaureester und/oder Borsäureesterderivate oder deren Verbindungen als Additive zugesetzt werden.Secondary batteries, especially those with solid polymer solutions, characterized in that boric acid esters and / or boric acid ester derivatives or their compounds are added as additives.
2. Verfahren nach Anspruch 1 , dadurch gekennzeichnet, daß die Borsaureester und/oder Borsäureesterderivate als Lithium-Verbindungen in Komplexen der Formeln2. The method according to claim 1, characterized in that the boric acid esters and / or boric acid ester derivatives as lithium compounds in complexes of the formulas
und/oder and or
π und/oder π and or
vorliegen, wobei die Restgruppen Ri und R2 aromatisch und/oder aliphatisch sein können und in Formel III M ein Ubergaπgsmetall ist und die Cyclopentadienyl-Gruppen auch Fluor anstelle von H tragen könnenare present, where the residual groups R 1 and R 2 can be aromatic and / or aliphatic and in formula III M is a transition metal and the cyclopentadienyl groups can also carry fluorine instead of H.
Verfahren nach einem oder mehreren der Ansprüche 1 bis 2, dadurch gekennzeichnet, daß die Additive an der Anodenseite zugesetzt werdenMethod according to one or more of claims 1 to 2, characterized in that the additives are added on the anode side
Verfahren nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die Additive in Mengen von großer als 0 bis 20 Gew %, vorzugsweise 5 Gew % bis 15 Gew %, zugegeben werdenProcess according to one or more of claims 1 to 3, characterized in that the additives are added in amounts of greater than 0 to 20% by weight, preferably 5% to 15% by weight
Anode zur Anwendung in galvanischen Zellen, insbesondere in Lithiumionen- Sekundarbatteπen und solchen mit festen Polymerlosungen, dadurch gekennzeichnet, daß in der Anode Borsaureester und/oder Borsaureesterdeπvate oder deren Verbindungen als Zusätze enthalten sindAnode for use in galvanic cells, especially in lithium ion secondary batteries and those with solid polymer solutions, characterized in that boric acid esters and / or boric acid ester derivatives or their compounds are contained as additives in the anode
Anode nach Anspruch 5 dadurch gekennzeichnet daß lithierte Borsaureester und/oder Borsaureesterdeπvate in Form komplexer Verbindungen der Formeln Anode according to claim 5, characterized in that lithiated boric acid esters and / or boric acid ester derivatives in the form of complex compounds of the formulas
und/oderand or
π und/oder π and / or
als Zusätze enthalten sind. are included as additives.
7. Anode nach Anspruch 5 und/oder 6, dadurch gekennzeichnet, daß die Zusätze in Mengen von größer als 0 bis 20 Gew.%, vorzugsweise 5 Gew.% bis 15 Gew.%, enthalten sind. 7. Anode according to claim 5 and / or 6, characterized in that the additives are contained in amounts of greater than 0 to 20% by weight, preferably 5% by weight to 15% by weight.
EP97953650A 1996-12-23 1997-12-19 Method and anode for improving the power density of lithium secondary batteries Withdrawn EP0948826A1 (en)

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DE19654057A DE19654057C2 (en) 1996-12-23 1996-12-23 Process for improving the power density of lithium secondary batteries
DE19654057 1996-12-23
PCT/DE1997/002974 WO1998028807A1 (en) 1996-12-23 1997-12-19 Method and anode for improving the power density of lithium secondary batteries

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KR100553736B1 (en) * 1999-09-02 2006-02-20 삼성에스디아이 주식회사 Composition of active material for lithium secondary batteries
EP1292633A4 (en) 2000-06-16 2003-07-23 Univ Arizona State Conductive polymeric compositions for lithium batteries
US7527899B2 (en) 2000-06-16 2009-05-05 Arizona Board Of Regents For And On Behalf Of Arizona State University Electrolytic orthoborate salts for lithium batteries
KR20020023145A (en) 2000-09-21 2002-03-28 가나이 쓰도무 Organic borate lithium compounds and nonaqueous electrolytes using the same
JP5666225B2 (en) * 2010-09-16 2015-02-12 株式会社豊田中央研究所 Negative electrode for lithium ion secondary battery and lithium ion secondary battery
CN102964369B (en) * 2012-10-24 2016-04-06 中国科学院青岛生物能源与过程研究所 One class in polymer type boric acid ester lithium salts and its preparation method and application
CN104183867B (en) * 2014-08-12 2018-06-19 中国科学院青岛生物能源与过程研究所 A kind of single ion conductor nano-particle reinforcement lithium battery diaphragm or method for preparing polymer electrolytes and application

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