Surface-stabilized and prelithiated anode active materials for lithium batteries and production method

Abstract

A prelithiated and surface-stabilized anode active material for use in a lithium battery, comprising a protected anode active material particle comprising a surface-stabilizing layer embracing a core particle, wherein the surface-stabilizing layer comprises a lithium- or sodium-containing species chemically bonded to the core particle and the lithium- or sodium-containing species is selected from Li2CO3, Li2O, Li2C2O4, LiOH, LiX, ROCO2Li, HCOLi, ROLi, (ROCO2Li)2, (CH2OCO2Li)2, Li2S, LixSOy, Li4B, Na4B, Na2CO3, Na2O, Na2C2O4, NaOH, NaiX, ROCO2Na, HCONa, RONa, (ROCO2Na)2, (CH2OCO2Na)2, Na2S, NaxSOy, or a combination thereof, wherein X=F, Cl, I, or Br, R=a hydrocarbon group, 0<x≤1, and 1≤y≤4; wherein the lithium- or sodium-containing species is preferably derived from an electrochemical decomposition reaction and the core particle is prelithiated to contain an amount of lithium from 1% to 100% of the maximum lithium content that can be included in the core particle of anode active material.

Description

FIELD OF THE INVENTION[0001]The present invention provides a method of producing an anode active material and anode electrode for a secondary battery, particularly a rechargeable lithium-ion or lithium metal battery that comprises an anode containing a surface-stabilized prelithiated anode active material.BACKGROUND[0002]Concerns over the safety of earlier lithium secondary batteries led to the development of lithium ion secondary batteries, in which pure lithium metal sheet or film was replaced by carbonaceous materials as the negative electrode (anode). The carbonaceous material may comprise primarily graphite that is intercalated with lithium and the resulting graphite intercalation compound may be expressed as LixC6, where x is typically less than 1. In order to minimize the loss in energy density due to this replacement, x in LixC6 must be maximized and the irreversible capacity loss Qir in the first charge of the battery must be minimized. The maximum amount of lithium that ca...

AI Technical Summary

Benefits of technology

The present invention provides a new material for the anode of a lithium battery that improves its capacity and lifespan. The material is prelithiated in a separate reactor and then deposited onto a surface-stabilizing layer using another reactor. This two-step process reduces equipment costs and saves time. The first step involves electrochemical prelithiation in a reactor, which may be the same as the second step. Overall, this patent describes a more efficient and effective method of making anode materials for lithium batteries.

Problems solved by technology

On repeated charge and discharge operations, the alloy particles tend to undergo pulverization and the current collector-supported thin films are prone to fragmentation due to expansion and contraction of the anode active material during the insertion and extraction of lithium ions.

This pulverization or fragmentation results in loss of particle-to-particle contacts between the active material and the conductive additive or contacts between the anode material and its current collector.

These adverse effects result in a significantly shortened charge-discharge cycle life.

In fact, most of prior art composite electrodes have deficiencies in some ways, e.g., in most cases, less than satisfactory reversible capacity, poor cycling stability, high irreversible capacity, ineffectiveness in reducing the internal stress or strain during the lithium ion insertion and extraction cycles, and some undesirable side effects.

These prior art materials do not offer a high lithium insertion capacity and this capacity also tends to decay rapidly upon repeated charging and discharging.

However, the notion that this amount of lithium that determines the battery capacity is totally supplied from the cathode, limits the choice of cathode active materials because the active materials must contain removable lithium.

In particular, these delithiated products tend to react with the electrolyte and generate heat, which raises safety concerns.

These changes in potential may give rise to parasitic reactions on both electrodes, but more severely on the anode.

However, as the SEI layer is formed, a portion of the lithium introduced into the cells via the cathode is irreversibly bound and thus removed from cyclic operation, i.e. from the capacity available to the user.

A further drawback is that the formation of the SEI layer on the anode after the first charging operation may be incomplete and will continue to progress during the subsequent charging and discharge cycles.

Even though this process becomes less pronounced with an increasing number of repeated charging and discharge cycles, it still causes continuous abstraction, from the system, of lithium which is no longer available for cyclic operation and thus for the capacity of the cell.

Additionally, as indicated earlier, the formation of a solid-electrolyte interface layer consumes about 10% to 30% of the amount of lithium originally stored at the cathode, which is already low in capacity (typically <200 mAh / g).

However, prelithiated carbon- or graphite-based anode active materials lead to electrodes which can be handled only under non-oxidizing and dry conditions, making practical production of lithium ion batteries difficult.

Such an additional electrode makes the battery very complicated and difficult to make.

Switching between two orientations is not a good strategy since it would complicate the handling of the battery and an average consumer would not pay attention to such a detail to ensure proper operation of such a battery.

Again, this additional electrode further complicates the manufacture and operation of a resulting battery.

The resulting multi-component, multi-phase mixture is still sensitive to the presence of oxygen and water contents in the air, thus significantly complicating the battery manufacturing operations.(4) In a follow-on patent application, Gao, et al.

Both the discrete lithium metal particles and lithiated carbonaceous material (graphite) are unstable in an oxygen- or moisture-containing environment.

Furthermore, Gao, et al. have not fairly suggested how other anode active materials than graphite can be prelithiated in a controlled manner (e.g., without inducing a lithium coating on the surface of active material particles).

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