CN112289973A - Lithium ion battery pack and method of manufacturing the same - Google Patents

Lithium ion battery pack and method of manufacturing the same Download PDF

Info

Publication number
CN112289973A
CN112289973A CN202010709331.8A CN202010709331A CN112289973A CN 112289973 A CN112289973 A CN 112289973A CN 202010709331 A CN202010709331 A CN 202010709331A CN 112289973 A CN112289973 A CN 112289973A
Authority
CN
China
Prior art keywords
layer
lithium
ion battery
active material
coated
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.)
Pending
Application number
CN202010709331.8A
Other languages
Chinese (zh)
Inventor
E·约希勒
T·施拉特
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Volkswagen AG
Original Assignee
Volkswagen AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Volkswagen AG filed Critical Volkswagen AG
Publication of CN112289973A publication Critical patent/CN112289973A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L50/00—Electric propulsion with power supplied within the vehicle
    • B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
    • B60L50/60—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by batteries
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L50/00—Electric propulsion with power supplied within the vehicle
    • B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
    • B60L50/60—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by batteries
    • B60L50/64—Constructional details of batteries specially adapted for electric vehicles
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • 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
    • 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
    • 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
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Power Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Transportation (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Energy (AREA)
  • Inorganic Chemistry (AREA)
  • Sustainable Development (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)
  • Battery Mounting, Suspending (AREA)

Abstract

Lithium ion batteryA battery cell and a method of manufacturing the same. The invention relates to a lithium ion battery cell (10) having a cathode (14) with a current collector (14 a) and LiNi coated on the current collector (14 a)0.5Mn1.5O4As a cathode active material (14 b), a first layer (18) composed of lithium niobium oxide is coated on the cathode active material (14 b), and a second layer (20) composed of lithium phosphate is coated on the first layer (20). The invention also relates to a method for producing such a lithium-ion battery cell (10) and to an electrically driven motor vehicle (2).

Description

Lithium ion battery pack and method of manufacturing the same
Technical Field
The invention relates to a lithium ion battery cell having a cathode with LiNi0.5Mn1.5O4As a cathode active material. The invention also relates to a method for manufacturing such a lithium ion battery cell.
Background
Lithium ion battery cells (Li-ion battery cells) have a plurality of anodes and cathodes, with separators disposed between the anodes and cathodes, respectively. In this case, the anode and the cathode each generally have a current collector, in particular a foil-like current collector, which has an active material (electrode material) coated thereon, into which lithium ions can be inserted (intercalated) and from which lithium ions can be extracted (transferred). The battery cell also has an electrolyte having a conductive salt, such as LiPF, dissolved therein6(lithium hexafluorophosphate); ethylene carbonate with a solvent, such as propylene carbonate; and if necessary with additional additives.
For example using a compound of the formula LiNixMnyCozO2As the active material of the cathode, the Lithium Nickel Cobalt manganese oxide (NMC), which is also referred to as cathode active material hereinafter, wherein x + y + z = 1 is preferably applied. In particular, nickel-rich lithium nickel cobalt manganese oxides, such as LiNi0.60Mn0.20Co0.20O2(NMC 622) or LiNi0.80Mn0.10Co0.10O2(NMC 811) has a relatively high specific capacity as a cathode active material. However, lithium nickel Cobalt manganese oxide is relatively expensive due to the presence of Cobalt (Cobalt) and due to the relatively high nickel content.
Alternatively thereto, lithium metal oxides having a spinel structure, in particular LiNi, are used0.5Mn1.5O4(LNMO) as a cathodeA polar active material. The lithium metal oxide is relatively easy to synthesize and has a relatively high energy density here. Disadvantageously, LiNi0.5Mn1.5O4The specific capacity of (a) is reduced relatively quickly. This is based on different mechanisms. Thus, for example, Mn of lithium metal oxide3+Can react in the presence of an electrolyte to form soluble Mn2+. Due to Mn2+The lithium metal oxide undergoes a phase transition from a spinel structure to a common salt structure, wherein intercalation and transfer of lithium ions do not occur in a region having such a common salt structure. Further, Mn2+Reach the anode by means of an electrolyte, in which Mn is present2+Is reduced to manganese metal at the anode, which results in the formation of a boundary layer, the so-called SEI (solid electrolyte membrane). In this case, such a boundary layer can prevent or at least limit the transfer of ions into or out of the anode active material.
Charging of lithium ion battery cells with relatively high voltages may also accelerate oxidation of the electrolyte on the cathode surface, where reaction products may build up on the electrodes making insertion (intercalation) and deintercalation (transport) of lithium ions difficult.
Such as "Research Progress in Improving the Cycling Stability of High-Voltage LiNi" in XiaoLong Xu et al0.5Mn1.5O4Lithium metal oxides, as generally represented in Cathode in Lithium-Ion batteries, Nano-micro-setters, 9(2), 22, may be doped or otherwise treated with inorganic materials, especially ZnO, Bi2O3Or Al2O3To coat.
Disclosure of Invention
The invention is based on the task of: a lithium ion battery cell is described in which capacity loss, in particular due to reaction of the cathode active material with the electrolyte and/or the evolution of manganese ions from the cathode active material is avoided or at least reduced. A method for producing such a lithium-ion battery cell and an electrically driven motor vehicle whose traction battery has such a lithium-ion battery cell are also to be described.
According to the invention, this object is achieved with regard to the lithium-ion battery cell by the features of claim 1. According to the invention, this object is achieved with respect to the method aspect by the features of claim 5, and with respect to the electrically driven motor vehicle aspect by the features of claim 7. Advantageous embodiments and embodiments are the subject matter of the dependent claims. Here, by contrast, the embodiments associated with the lithium-ion battery cell also apply to the method and to the motor vehicle, and vice versa.
The lithium ion battery cell has a cathode having a current collector and having LiNi coated on the current collector0.5Mn1.5O4As a cathode active material. Here, the cathode active material is used for: lithium ions are inserted into and extracted from the cathode active material. Furthermore, on the cathode active material, i.e., on LiNi0.5Mn1.5O4Coated with a first layer of lithium niobium oxide, also referred to as substrate-side layer.
A second layer, also referred to as an electrolyte-side layer, is applied to the first layer of lithium niobium oxide, wherein the second layer is formed by means of lithium phosphate. In this case, the lithium phosphate has a comparatively high electrochemical stability with respect to reaction with the electrolyte, so that protection is formed for the first layer and for the cathode active material by means of the second layer.
Here and in the following, the crystal axis is represented by "[ ]" and an axis equivalent to the axis is represented by "< >".
The substrate-side layer, i.e., the first layer, of lithium niobium oxide has a structure similar to LiNi0.5Mn1.5O4Higher crystalline compatibility. In other words, the crystal symmetry and/or lattice parameters of the lithium niobium oxide, such as the edge length of the cells and/or the angle between the edges of the cells, with respect to at least one (lattice plane) crystal interface and LiNi0.5Mn1.5O4Either onlyWith comparatively slight deviations, in particular deviations of less than 5%.
Further, in the case of the material combination presented above, the difference between not only the elastic modulus, the compressive modulus, and the shear modulus of the first layer and the cathode active material is small, but also the difference between the elastic modulus, the compressive modulus, and the shear modulus of the first layer and the second layer is small. In this way, layer failures, such as peeling, tearing or breaking of the first layer and/or the second layer, are avoided or the risk of said layer failure is at least reduced when the coated cathode active material is subjected to mechanical loads.
On the basis of this and on the basis of the crystalline compatibility of the first layer with the second layer and of the first layer with the cathode active material, a comparatively high mechanical stability of the coated cathode active material is advantageously achieved.
For example, the lithium-ion battery pack is provided and set up for a traction battery pack of an electrically driven motor vehicle, which traction battery pack supplies electrical energy to an electric machine for driving the motor vehicle.
The lithium niobium oxide of the first layer is, for example, Li3NbO4Or LiNbO2. However, according to a preferred embodiment, the lithium niobium oxide of the first layer is LiNbO3(lithium niobate). Advantageously, the lithium niobate has its [100 ]]Of crystal axis with cathode active material [110 ]]The crystallographic uniformity of the crystal axes or only slight deviations. Advantageously, the lithium niobate also has a relatively high ionic conductivity, which is greater than 10-6S/cm (Siemens per centimeter).
In this case, phosphate is to be understood as orthophosphoric acid (H)3PO4) Salts and esters, and condensates (polymers) of orthophosphoric acid and esters of the condensates. For example, lithium phosphate has the formula Li3PO4. However, according to a preferred embodiment, lithium pyrophosphate, i.e. Li, is used4P2O7As lithium phosphate. Advantageously, lithium pyrophosphate has a relatively high electrochemical stability, the electrochemical window (voltage window) of which is greater than 5V. Thus, by means ofIn the second layer, a stable protection against oxidation or reduction is formed against reaction with the electrolyte, both for the cathode active material and for the first layer. Advantageously, lithium pyrophosphate also has a relatively high ionic conductivity, which is greater than 10-3S/cm (Siemens per centimeter).
According to an advantageous embodiment, the layer thickness of the first layer and/or the second layer is between 0.5nm and 2nm, respectively. Preferably, the layer thicknesses are each 1 nm. In this context, the layer thickness of a layer is to be understood in particular as the extent of the layer in a direction perpendicular to the side on which the layer is applied. Advantageously, due to this comparatively small layer thickness, neither the insertion nor the extraction of lithium ions into or from the cathode active material is influenced or only slightly influenced.
According to a method for manufacturing a lithium ion battery cell constructed according to one of the variants presented above, first a LiNi is provided0.5Mn1.5O4I.e., lithium metal oxide having a spinel structure, as a cathode active material. Suitably, LiNi0.5Mn1.5O4Is provided in powder form. Namely LiNi0.5Mn1.5O4By means of a large number of (powder) particles.
Subsequently, LiNi is treated with a first layer consisting of lithium niobium oxide, preferably consisting of lithium niobate0.5Mn1.5O4I.e., the cathode active material. Accordingly, in LiNi0.5Mn1.5O4A layer composed of lithium niobium oxide or composed of lithium niobate is disposed thereon as a first layer. Thus, LiNi0.5Mn1.5O4The powder particles are provided with the first layer.
Next, LiNi coated with the first layer is coated with a second layer composed of lithium phosphate, preferably lithium pyrophosphate0.5Mn1.5O4And (6) coating. In other words, the second layer is applied to the first layer. Here, advantageously, since for LiNi0.5Mn1.5O4Coating the powder particles to obtainComplete encapsulation of the respective particles by these two layers is now used.
LiNi to be coated with the first layer and with the second layer0.5Mn1.5O4Is applied to the current collector. For example, the coated cathode active material is mixed with binders, with solvents and, if appropriate, with electrically conductive, electrically conductive additives, such as, in particular, electrically conductive carbon black, aluminum powder or nickel powder. Next, the mixture is coated on a current collector and dried while forming a cathode. Here, for example, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose or hydroxypropyl cellulose are used as binders, and for example N-methyl-2-pyrrolidone is used as a solvent.
In summary, LiNi0.5Mn1.5O4The powder particles are provided with two superposed layers, which are also referred to as cover layers. In this case, the second layer, i.e. the outer layer with respect to the respective particles, is surrounded by the electrolyte in the assembled state of the lithium ion battery cell. The first, inner layer is disposed between the second layer and LiNi0.5Mn1.5O4Between the powder particles. The second layer has a comparatively high electrochemical stability and, with it, a high protective action against the cathode active material and against the first layer with respect to reaction with the electrolyte. In this case, the coating of the second layer is advantageously simplified due to the crystallographic consistency of the second layer with the first layer presented above. In addition, the second layer can be formed relatively thinly, so that the electrical conductivity of the cathode is only reduced correspondingly slightly.
Alternatively, the cathode active material is first coated on the current collector. For this purpose, the cathode active material is expediently mixed with binders, with solvents and, if appropriate, with conductive additives, applied to the current collector and subsequently dried, as presented above. According to this alternative embodiment, the cathode active material and the binder and, if appropriate, the conductive additive applied to the current collector are then coated with the first layer and subsequently with the second layer.
For applying the first layer and/or the second layer, for example, a so-called sol-gel process or a wet-chemical process or a dry-chemical process is used. Alternatively, the corresponding layer is, for example, used in the synthesis of LiNi0.5Mn1.5O4By adding corresponding precursors, for example by means of corresponding layers, to the LiNi0.5Mn1.5O4And surface segregation during calcination of the mixture of these precursors. However, according to an advantageous embodiment, a vapor deposition method is used for applying the first layer and/or the second layer. Preferably, an Atomic Layer Deposition (ALD) method is used. In this way, relatively thin layers, in particular layers having a layer thickness of less than 2nm, can be achieved, wherein the chemical composition of the layers can be controlled and/or adjusted relatively well in the case of atomic layer deposition.
According to one advantageous embodiment, the electrically driven motor vehicle has a traction battery pack. The traction battery pack in turn comprises a lithium ion battery cell, preferably a plurality of lithium ion battery cells, each of which provides electrical energy for driving the motor vehicle in a manner suitable for an electric machine. The respective lithium ion battery cell is configured according to one of the variants of the lithium ion battery cell presented above and/or is produced according to one of the variants of the method for producing a lithium ion battery cell presented above.
Drawings
Subsequently, embodiments of the invention are further elucidated on the basis of the drawing. Wherein:
fig. 1 shows a schematic representation of a motor vehicle having a traction battery whose lithium-ion battery cells each have a plurality of cathodes with LiNi0.5Mn1.5O4As a cathode active material;
fig. 2 schematically shows a particle of a cathode active material in which a first layer composed of lithium niobate is coated onto the particle and a second layer composed of lithium pyrophosphate is coated onto the first layer; and
fig. 3 shows a method flow for producing one of the lithium-ion battery cells in a flow chart.
Throughout the drawings, parts and parameters corresponding to each other are provided with the same reference numerals throughout.
Detailed Description
The motor vehicle 2 shown in fig. 1 is electrically driven. For this purpose, the motor vehicle 2 has an electric machine 4, which is connected to a traction battery pack 8 via an inverter 6. The traction battery 8 has a plurality of battery cells 10, which are wired to one another and connected to the inverter 8. In this case, only two of the lithium ion battery cells 10 are shown for clarity.
In each of these lithium ion battery cells 10, anodes 12 and cathodes 14 are stacked alternately one above the other, wherein a separator 16 is arranged between each anode 12 and cathode 14, such that the anodes 12 and cathodes 14 are spatially separated from one another. In fig. 1, the membrane 16 is represented in shadow and has, for example, polyethylene and/or polypropylene.
Each of these anodes 12 has an anode foil, which is embodied, for example, as a copper foil, as a current collector 12a, which is coated on both sides, i.e., on the flat side of the current collector, with an anode active material 12b (active material of the anode), for example, graphite.
Each of these cathodes 14 has a cathode foil, for example, an aluminum foil, as a current collector 14 a. A cathode active material 14b (active material of the cathode) is coated on both sides of the current collector. Here, the cathode active material 14b, i.e., the active material of the cathode 14, is made of a lithium metal oxide having a spinel structure, i.e., LiNi0.5Mn1.5O4To form the composite material.
Here, the cathode active material 14b is formed of a large number of particles on which lithium niobium oxide (LiNbO) is coated, respectively3) I.e., the first layer 18 of lithium niobate, and lithium pyrophosphate (Li), which is lithium phosphate4P2O7) A second layer 20 is formed. In other words, the particles are made of lithium niobate respectivelyA first layer 18 and is coated with a second layer 20 of lithium pyrophosphate. In fig. 1, the cathode active material 14b coated with the first layer 18 and with the second layer 20 is represented as flat dots. In fig. 2, one of the particles coated with the first layer 18 and with the second layer 20 is schematically shown.
In addition, a liquid electrolyte, not further shown, is accommodated in each of these lithium ion battery cells 10. The liquid electrolyte has a conductive salt and a solvent for the conductive salt, wherein lithium hexafluorophosphate is exemplarily used as the conductive salt and a mixture of ethylene carbonate and diethyl carbonate is used as the solvent.
In fig. 2, one of the particles of the cathode active material 14b coated with the first layer 18 and with the second layer 20 is schematically shown. Here, the first layer 18 (on the substrate side) is arranged between the particles and the second layer 20. In this case, the second layer, i.e. the outer layer, is surrounded by the electrolyte in the assembled state of the lithium-ion battery cell 10. Here, the second layer 20 has a high electrochemical stability, has an electrochemical window (voltage window) of more than 5V, and consequently has a high protective effect against the cathode active material 14b and against the first layer 18 with respect to reaction with the electrolyte. Due to Li4P2O7Is (001)]Crystal axis and LiNbO3Of (1) [100 ]]Crystal axis, Li4P2O7Of [111 ]]Crystal axis and LiNbO3Of [101 ]]Crystal axis and Li4P2O7[010 ] of]Crystal axis and LiNbO3Is (001)]The crystallographic uniformity of the crystal axes or only slight deviations, the application of the second layer 20 is simplified.
For better recognition, fig. 2 is not to scale. Thus, the maximum extension a of the particles (particle size) is between 0.5 μm and 20 μm. The layer thickness b of the first layer 18 and the layer thickness c of the second layer 20 are between 0.5nm and 2 nm.
The flow chart shown in fig. 3 represents a method flow for producing a lithium-ion battery cell 10, in particular one of the lithium-ion battery cells 10 of an electrically driven motor vehicle 2.
In this case, in the first step I, the cathode active material 14b supplied as a powder, that is, LiNi, is subjected to the use of the first layer 18 composed of lithium niobate0.5Mn1.5O4And (6) coating. In other words, the first layer 18 is applied to LiNi0.5Mn1.5O4On the powder particles.
In a second step II, LiNi coated with the first layer 18 is coated with a second coating 20 consisting of lithium pyrophosphate0.5Mn1.5O4The powder particles are coated.
For the coating process of the first step I and the second step II, respectively, a vapor deposition method is used. Preferably, Atomic Layer Deposition (ALD) and corresponding precursors are used. In this way a layer thickness between 0.5nm and 2nm is achieved.
In a third step III, LiNi coated with a first layer 18 and with a second layer 200.5Mn1.5O4The powder particles are mixed with a binder, with a solvent and with a conductive additive, in particular conductive carbon black, aluminum powder or nickel powder, which is electrically conductive. The mixture is coated on the current collector 14a and dried while forming the cathode 14. Here, for example, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose or hydroxypropyl cellulose are used as binders, and for example N-methyl-2-pyrrolidone is used as a solvent.
The invention is not limited to the embodiments described above. Rather, other variants of the invention can also be derived therefrom by those skilled in the art without departing from the subject matter of the invention. Furthermore, in particular, all individual features described in connection with the embodiments can also be combined with one another in other ways without departing from the subject matter of the invention.
List of reference numerals
2 Motor vehicle
4 electric machine
6 inverter
8 traction battery pack
10 lithium ion battery cell
12 anode
12a anode foil/current collector
12b Anode active Material
14 cathode
14a cathode foil/current collector
14b cathode active Material
16 diaphragm
18 first layer
20 second layer
a stretching of particles of cathode active material
b layer thickness of the first layer
c layer thickness of the second layer
I coating of cathode active Material with a first layer
II coating the cathode active material coated with the first layer with a second layer
III coating the cathode active material coated with two layers onto a current collector.

Claims (7)

1. A lithium ion battery cell (10) having
-a cathode (14) having a current collector (14 a) and having LiNi coated on the current collector (14 a)0.5Mn1.5O4As a cathode active material (14 b),
-wherein a first layer (18) of lithium niobium oxide is applied on said cathode active material (14 b), and
-wherein a second layer (20) of lithium phosphate is coated on the first layer (18).
2. The lithium ion battery cell (10) of claim 1,
it is characterized in that the preparation method is characterized in that,
the lithium niobium oxide is lithium niobate.
3. The lithium ion battery cell (10) of claim 1 or 2,
it is characterized in that the preparation method is characterized in that,
the lithium phosphate is lithium pyrophosphate.
4. The lithium ion battery cell (10) according to any one of claims 1 to 3,
it is characterized in that the preparation method is characterized in that,
the layer thickness (b or c) of the first layer (18) and/or the second layer (20) is between 0.5nm and 2nm, in particular 1 nm.
5. A method for manufacturing a lithium ion battery cell (10) constructed according to any of claims 1 to 4,
-wherein LiNi as cathode active material (14 b) is paired with the first layer (18)0.5Mn1.5O4The coating is carried out, and the coating is carried out,
-wherein the LiNi coated with the first layer (18) is coated with the second layer (20)0.5Mn1.5O4Is coated and
-LiNi in which the coating is to be carried out with the first layer (18) and with the second layer (20)0.5Mn1.5O4Is applied to the current collector (14 a).
6. The method of claim 5, wherein the first and second light sources are selected from the group consisting of,
it is characterized in that the preparation method is characterized in that,
for applying the first layer (18) and/or the second layer (20), a vapor deposition method is used.
7. An electrically driven motor vehicle (2) having a traction battery pack (8) with a lithium ion battery cell (10) constructed according to any one of claims 1 to 4 and/or manufactured according to claim 5 or 6.
CN202010709331.8A 2019-07-22 2020-07-22 Lithium ion battery pack and method of manufacturing the same Pending CN112289973A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102019210857.1 2019-07-22
DE102019210857.1A DE102019210857A1 (en) 2019-07-22 2019-07-22 Lithium-ion battery cell and process for their manufacture

Publications (1)

Publication Number Publication Date
CN112289973A true CN112289973A (en) 2021-01-29

Family

ID=74098446

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202010709331.8A Pending CN112289973A (en) 2019-07-22 2020-07-22 Lithium ion battery pack and method of manufacturing the same

Country Status (2)

Country Link
CN (1) CN112289973A (en)
DE (1) DE102019210857A1 (en)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130260250A1 (en) * 2010-12-17 2013-10-03 Toyota Jidosha Kabushiki Kaisha Secondary battery
CN103548186A (en) * 2011-05-23 2014-01-29 丰田自动车株式会社 Positive electrode active material particles, and positive electrode and all-solid-state battery using same
WO2015102836A1 (en) * 2014-01-02 2015-07-09 Applied Materials, Inc. Solid state electrolyte and barrier on lithium metal and its methods
CN104934586A (en) * 2014-03-19 2015-09-23 丰田自动车株式会社 Active Material Powder And Method Of Producing The Same
CN106298270A (en) * 2016-11-02 2017-01-04 常州立方能源技术有限公司 A kind of positive plate of Asymmetric Supercapacitor and its preparation method and application
WO2018012522A1 (en) * 2016-07-14 2018-01-18 三井金属鉱業株式会社 Cathode active material for all-solid-state lithium secondary battery
JP2018125286A (en) * 2017-01-30 2018-08-09 セントラル硝子株式会社 Electrode laminate and all-solid lithium battery
US20190386322A1 (en) * 2017-03-14 2019-12-19 Fujifilm Corporation Solid electrolyte composition, solid electrolyte-containing sheet, all-solid state secondary battery, methods for manufacturing solid electrolyte composition, solid electrolyte-containing sheet, and all-solid state secondary battery
CN114937770A (en) * 2022-06-15 2022-08-23 厦门永力鑫新能源科技有限公司 Double-layer lithium ion conductor coated modified lithium cobaltate positive electrode material, preparation method thereof, lithium ion battery and electric equipment

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102016101013A1 (en) * 2016-01-21 2017-07-27 Von Ardenne Gmbh Method, coating apparatus and processing arrangement

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130260250A1 (en) * 2010-12-17 2013-10-03 Toyota Jidosha Kabushiki Kaisha Secondary battery
CN103548186A (en) * 2011-05-23 2014-01-29 丰田自动车株式会社 Positive electrode active material particles, and positive electrode and all-solid-state battery using same
WO2015102836A1 (en) * 2014-01-02 2015-07-09 Applied Materials, Inc. Solid state electrolyte and barrier on lithium metal and its methods
CN104934586A (en) * 2014-03-19 2015-09-23 丰田自动车株式会社 Active Material Powder And Method Of Producing The Same
US20150270537A1 (en) * 2014-03-19 2015-09-24 Toyota Jidosha Kabushiki Kaisha Active material powder and method of producing the same
WO2018012522A1 (en) * 2016-07-14 2018-01-18 三井金属鉱業株式会社 Cathode active material for all-solid-state lithium secondary battery
CN109478645A (en) * 2016-07-14 2019-03-15 三井金属矿业株式会社 Fully solid positive active material for lithium secondary battery
CN106298270A (en) * 2016-11-02 2017-01-04 常州立方能源技术有限公司 A kind of positive plate of Asymmetric Supercapacitor and its preparation method and application
JP2018125286A (en) * 2017-01-30 2018-08-09 セントラル硝子株式会社 Electrode laminate and all-solid lithium battery
US20190386322A1 (en) * 2017-03-14 2019-12-19 Fujifilm Corporation Solid electrolyte composition, solid electrolyte-containing sheet, all-solid state secondary battery, methods for manufacturing solid electrolyte composition, solid electrolyte-containing sheet, and all-solid state secondary battery
CN114937770A (en) * 2022-06-15 2022-08-23 厦门永力鑫新能源科技有限公司 Double-layer lithium ion conductor coated modified lithium cobaltate positive electrode material, preparation method thereof, lithium ion battery and electric equipment

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
HYEO NGWOO KIM, ET AL.: "A nano-LiNbO3coating layer and diffusion-inducedsurface control towards high-performance 5 Vspinel cathodes for rechargeable batteries", JOURNAL OF MATERIALS CHEMISTRY A, vol. 5, no. 47, 16 November 2017 (2017-11-16), pages 25077 *
JIN CHONG , ET AL.: "Surface stabilized LiNi0.5Mn1.5O4 cathode materials with high-rate capability and long cycle life for lithium ion batteries", NANO ENERGY, vol. 2, no. 3, 12 October 2012 (2012-10-12), pages 283 - 293 *

Also Published As

Publication number Publication date
DE102019210857A1 (en) 2021-01-28

Similar Documents

Publication Publication Date Title
JP7279115B2 (en) Nanoengineered coatings for anode active material, cathode active material and solid electrolyte, and methods of manufacturing batteries containing nanoengineered coatings
JP2024056867A (en) Compositions and methods for energy storage devices with improved performance - Patents.com
JP6612566B2 (en) Negative electrode for lithium ion non-aqueous electrolyte secondary battery, lithium ion non-aqueous electrolyte secondary battery, battery pack and automobile
KR100700711B1 (en) Hybrid electrical energy storage apparatus
US20200227723A1 (en) Compositions and methods for prelithiating energy storage devices
US20160172682A1 (en) Method for producing an electrode for a lithium-ion battery
CN111384399B (en) Protective coating for lithium metal electrodes
CN107112584B (en) Nonaqueous electrolyte secondary battery and positive electrode for nonaqueous electrolyte secondary battery
US20210257656A1 (en) Lithium phosphate coating for lithium lanthanum zirconium oxide solid-state electrolyte powders
DE102020129335A1 (en) PROCESS FOR LITHIZING ELECTROACTIVE MATERIALS
KR20190025664A (en) Electrolyte
KR101664629B1 (en) Method for preparing bi-polar all solid battery
JP2013247009A (en) Manufacturing method of nonaqueous electrolyte secondary battery
CN106654168B (en) Nonaqueous electrolyte secondary battery and method for producing same, and conductive assistant for nonaqueous electrolyte secondary battery and method for producing same
JP2013084420A (en) Laminated lithium-ion battery
DE102022120235A1 (en) SOLID STATE SYNTHESIS FOR THE MANUFACTURE OF A LAYERED ANODE MATERIAL
JP2010251194A (en) Positive electrode for battery and method of manufacturing the same
DE102022109020A1 (en) OVERLITHIATED CATHODE MATERIALS AND PROCESS FOR THEIR PRODUCTION
CN112289973A (en) Lithium ion battery pack and method of manufacturing the same
US20170033363A1 (en) Method for producing an electrode of a lithium-ion battery
JP2022077319A (en) Anode active material
US20230216031A1 (en) Cathode Active Material, and Lithium Ion Battery Comprising Said Cathode Active Material
CN106328912A (en) Anode for a battery cell, method for manufacturing an anode, and battery cell
JP2023535268A (en) Cathode active material and lithium ion battery with cathode active material
US20220271277A1 (en) Hybrid electrode

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination