What is claimed is:

Design or demand specifications deter mine material parameters for a recycled battery by identi fying a molar ratio and elements of cathode materials corresponding to a charge material chemistry of a recycled battery.

For the recovery and synthesis of LiNiCoAlO. there are at least two approaches.

it is desirable that the batteries be of a single stream chemistry (LiNiCoAlO) however if there are other chemistries present in the LiMO (where M is manganese, as well as Ni, Al and Co), the manganese can be removed from Solution. Ni, Co and Al can be used to precipitate precursor and synthesize cathode materials.

Battery chemistries including aluminum (Al) are becoming popular for applications such as electric vehicles, using chemistry Such as LiNiCoAlO. Conventional approaches for recovering active materials from lithium ion batteries with chemistry LiNiCoAlO in a manner that can be used to make new active materials for new lithium ion batteries have been met with several shortcomings.

It can be complex to sort out lithium ion batteries based on the battery chemistry and conventional methods cannot effectively recycle lithium ion batteries with mixed chemistries because different procedures are required to separate the respective compounds for reuse as active cath ode material.

with the development of lithium ion battery technologies, different cathode materials are now being used to produce lithium ion batteries Such as LiCoO, LiFePO, LiMnO, LiNiCo, Al-O, and LiNi,Mn, Co-O.

Primary functional parts of the lithium-ion battery 140 are the anode 160, cathode, 162 electrolyte 168, and separator 172. LIBs use an intercalated lithium compound as the electrode materials.

Physical separation is applied to remove the battery cases (plastic) and electrode materials, often via magnetic separation that draws out the magnetic steel.

The proposed approach is an example and is applicable to other lithium and non-lithium batteries for recycling spent batteries and recovering active cathode material suitable for use in new batteries.

is a process flow diagram of recycling lithium-aluminum ion batteries

is a diagram of recycling the cathode material in the battery

FIG. 1 is a context diagram of a battery recycling environment Suitable for use with configurations herein;

It should be noted that although the methods and apparatus disclosed herein employ Li-ion bat teries as an example, the principles are intended as illustra tive and could be applied to other types of cathode materials suited to other battery chemistries.

The recovered precursor material NiCoAl(OH) or NiCo(OH) can be used for making new LiNiCoAlO, or LiNiCoO cathode materials.

he solution includes recovering active materials from lithium ion batteries with LiNiCoAlO. chemistry in a manner that can be used to make new active materials for new lithium ion batteries.

Unfortunately, conventional approaches to the above approaches Suffer from the shortcoming that recycling approaches include high temperature processes to separate the compounds of the desirable materials of cobalt, manga nese, nickel and lithium.

While 97% of lead acid batteries are recycled, such that over 50 percent of the lead supply comes from recycled batteries, lithium ion batteries are not yet being recycled widely.

The disclosed approach results in synthesis of cathode materials (particularly valuable in Li-ion batteries) from recycled components. In contrast to conventional approaches, the disclosed approach does not separate Ni, Mn, and Co out. Instead, uniform-phase pre cipitation is employed as starting materials to synthesize the cathode materials as active charge material Suitable for new batteries.

Current recycling procedures for Li-ion cells are generally focused on LiCoO cathode materials. Although some posted their methods to recycle more kinds of cathode materials, all are complex and not necessarily economical or practical.

In short, recycling of lithium ion batteries not only protects the environment and saves energy, but also presents a lucrative outlet for battery manufacturers by providing an inexpensive Supply of active cathode material for new batteries.

Additionally, battery disposal would require that fresh metals be mined for cathode material, and mining has a much bigger environmental impact and cost than simple recycling would.

Recycling of the charge material in the lithium batteries both reduces waste volume and yields active charge material for new batteries

Lithium-ion batteries, like their NiCd (nickel-cad mium) and NiMH (nickel-metal hydride) predecessors, have a finite number of charge cycles.

Exhausted LIBs undergo a physical separation pro cess for removing Solid battery components, such as casing and plastics, and electrodes are dissolved in a solution for extracting the useful elements Co (cobalt), Ni (nickel), Mn (manganese), and Li (lithium), from mixed cathode materi als and utilizing the recycled elements to produce active materials for new batteries

Modern elec tronics, however, place significantly greater demands on the longevity and mass of batteries.

Recently, however, advances in lithium-ion batteries (LIBs) have been signifi cant such that they have become the most popular power Source for portable electronics equipment, and are also growing in popularity for military, electric vehicle, and aerospace applications

Modern electronic devices, such as cell phones, computing devices, and automobiles, demand substantial current delivery while being lightweight and Small enough to avoid hindering the portability of the host device.

For decades, portable electrical power supplies have taken the form of batteries that release electrical energy from an electrochemical reaction.

Cathode material from exhausted lithium ion batteries are dissolved in a solution for extracting the useful elements Co (21) Appl. No.: 15/358,862 (cobalt), Ni (nickel), Al (Aluminum) and Mn (manganese) to (22) Filed: Nov. 22, 2016 produce active cathode materials for new batteries.

Al battery pouch cellsduringbattery operation and observed no safety hazard, owing to the lack offlammability of the ionic liquid electrolyte in air

We have developed a new Al-ion battery using novel graphitic cath-odematerialswithastablecyclinglifeupto7,500charge/dischargecycleswithout decay at ultrahigh current densities.

We propose that simplified Al/graphite cell redox reactions duringcharging and discharging can be written as

Because high-rate and high-power batteries are highly desirable forapplications such as electrical grid storage, the next step in the investi-gation was to developa cathode material that wouldhave reduced ener-getic barriers to intercalation during charging

Rechargeable Al/graphite cel

Owing to the low-cost, low-flammability and three-electron redoxproperties of aluminium (Al), rechargeable Al-based batteries could inprincipleoffer cost-effectiveness,highcapacity and safety, which wouldlead to a substantial advance in energy storage technology

Rechargeable aluminium-based batteries offer the possibilities oflow cost and low flammability, together with three-electron-redoxproperties leading to high capacity

Thedevelopmentofnewrechargeablebatterysystemscouldfuelvar-iousenergyapplications, frompersonalelectronics togridstorage

The reason why we are facing the present global energy and environment crisis is due to the fact that we have violated the time–matter cycle by rapidly consuming for the past 200  years fossil fuels that took millions of years to be formed and accumulated.

Moreover, the chemistry of recycling will become more important than ever and let’s hope that chemists can successively give a second life to wastes. Undoubtedly, sustainable batteries can be made and bring major advances in the protection of our environment, provided we realize such an effort is only worthwhile if we use CO2-free electricity.

This has resulted in the enabling of new plans and programmes that tackle shortcom-ings and take into consideration energy and development. Most of these programmes stress the importance of education, research and public funding to achieve sustainable production and consumption patterns.

Until an alter-native can be found, it will be necessary to design batteries with suf-ficient confinement in the event of cell malfunction

Concerns regarding the ‘green’ quality of batteries have long existed and over the years these concerns have been addressed in a vari-ety of ways. We must now address the issue of chemical toxicity in batteries head-on by identifying non-toxic element and additive alternatives with similar performance to their toxic counterparts

The reason why we are facing the present global energy and environment crisis is due to the fact that we have violated the time–matter cycle by rapidly consuming for the past 200  years fossil fuels that took millions of years to be formed and accumulated.

d, the main ones being pyro-metallurgy and hydrometallurgy processes, which proceed at high (pyrolysis) and low (solution chemistry) temperatures, respec-tively.

d, the main ones being pyro-metallurgy and hydrometallurgy processes, which proceed at high (pyrolysis) and low (solution chemistry) temperatures, respec-tively.

Although ‘recycling chemistry’ is not particularly fashionable today, it encompasses a discipline that is very important for the future of our planet.

Li-ion batteries do not contain any of these materials but 3d metals such as nickel or cobalt are used in most of them. Their use together with lithium is problematic due to limited supply, their continuously increasing cost and the environ-mentally questionable extraction methods.

The recycling process of e-waste should reduce scrap volume, separate battery components and enrich valuable metals, and eliminate or reduce the danger of waste release to the environment.

Li-ion batteries do not contain any of these materials but 3d metals such as nickel or cobalt are used in most of them. Their use together with lithium is problematic due to limited supply, their continuously increasing cost and the environ-mentally questionable extraction methods.

Several hundred thousand tons of batteries are sold annually; this constitutes an ‘urban mine’ for the recovery of thousands of tons of metal with cost advantages over direct mining.

A systematic extrapolation of our Li-ion knowledge will therefore not be sufficient, as it has already been shown that the best electrolyte additive for Li-ion cells (vinylidene carbonate) drastically increases the lifetime of Li-ion cells, but has no effect on Na-ion ones.

The foreseen demand for lithium, dictated by the expanding electric vehicle and grid applications, brings fear of lithium shortage. It also raises geopolitical issues related to uneven global distribution of lith-ium around the world.

Such findings, although not viable for practical applications, have at least the merit to demonstrate that such a system can work and be made practical provided further breakthroughs are made in terms of elec-trolytes and catalysts.

Li–O2 and Li–S. Another option towards more sustainable bat-tery systems is moving to metal–air systems (Li–, Na– and Mg–air batteries) using O2 as the positive electrode, which is similar to the concept of fuel cells

These challenges call for a collaborative effort between inorganic, organic and biochemists to develop innovative and diversified syn-thetic approaches to optimize existing materials and design new materials for batteries.

Organic batteries with minimal CO2 footprints, assuming all other challenges (materials solubility, finding a highly oxidizing Li-based positive electrode, and so on) are overcome, should ena-ble the use of Li-ion batteries for large-scale applications

A great advantage of the Li-ion battery, as opposed to Pb–acid, Ni–Cd and Ni–metal hydride batteries, is its versatility with respect to the wide range of positive and nega-tive electrodes that can be used, which offers possibilities in terms of designing new high-performance electrodes based on low-cost

Mismatch between the elements constituting biomass and the main constituents of our present Li-ion batteries.

This strongly validates the move towards post-Li chemistries based on sodium and potassium, and encourages increased efforts on mag-nesium and calcium chemistries.

Mismatch between the elements constituting biomass and the main constituents of our present Li-ion batteries.

attery technologies versus element abundanceThe abundance of an element is just one of the many criteria con-trolling its cost and availability.

There are various approaches that have been explored towards this goal: (1) the development of novel eco-efficient processes18such as hydro-, solvo- and ionothermal19,20 and bio-inspired21–23approaches for the synthesis of inorganic compounds; (2) the pro-motion of a new concept of renewable electrodes based on the use of organic compounds synthesized using ‘green chemistry’24,25 from natural resources; and (3) the development of new technologies beyond Li-ion batteries such as Li–S and Li–air (Li–O2; ref.  26), Al–air27, Na-ion28, Mg, Ca29 and redox-flow systems30, in combina-tion with an increasing interest in recycling processes. Li–O2 cells are often synonymously called Li–air cells even though they cur-rently use pure O2 rather than ‘air’.

the only viable path towards a ‘greener and more sustainable’ battery is rooted in our ability to design electroactive materials that have comparable performances to today’s electrodes, but cost less energy and release less CO2 during production.

Energy required for the production of a 1 kWh electrochemical storage system

batteries will only begin to have an environmental benefit beyond hundreds of cycles. This also questions the benefits of developing batteries for electric vehi-cles to decrease greenhouse-gas emissions when we heavily rely on coal-fired plants to produce primary electricity.

developing Li-ion batteries for transport and that are able to deal with society’s fluctuating energy needs is a formidable chal-lenge, especially from a materials perspective. In addition to the classical figures of merit (specific energy and power, lifetime, cost and safety), other issues are not yet fully recognized, such as the low relative abundance of materials (lithium is already viewed by some alarmists as the gold of this next century) and the large energy cost of battery manufacture and recycling.

The attractiveness of Li-ion battery technology resides in its ver-satility; it covers a wide range of applications requiring dozens of watt-hours (portable electronics), dozens of kilowatt hours (elec-tric vehicles) and tens of megawatt-hours (grid applications), with design capabilities to meet autonomy and power requirements

It is essential to consider sustainability, renewability and ‘green chemistry’4 when selecting materials for storage devices (for example, electrodes, catalysts), especially when used in applications with large markets and volume (vehicles, grid).

Past, present and forecast of the world’s energy needs up to 2050.

the most important consideration in our market econ-omy is the cost associated with producing conversion and stor-age devices

If we are unsuccessful in jointly capturing, managing and storing energy at a large scale and low cost, our only recourse will be to drastically reduce our total energy consumption.

we currently only have the capacity to store around 1% of the energy consumed worldwide, most of which (98%) is through pumped-storage hydroelectricity

It is therefore essential to incorporate material abun-dance, eco-efficient synthetic processes and life-cycle analysis into the design of new electrochemical storage systems.

Ever-growing energy needs and depleting fossil-fuel resources demand the pursuit of sustainable energy alternatives, includ-ing both renewable energy sources and sustainable storage technologies

In short, we require methods to establish the health record of the battery, analogous to personal health records for human beings.

New methods must be developed that will allow batteries to be controlled and traced so that they can be used for more than one application.

We need new analytical methods, optimized to probe specific battery chemistries, so that new technologies can be brought to the market more rapidly to meet societal demands.

New sustainable technologies beyond Li-ion technology have been explored. Among those that use the more abundant monova-lent (Na+) and divalent (Mg2+, Ca2+) ions, Na-ion technology holds great promise for future commercialization. In contrast, the future of Mg-ion technology is more uncertain, owing to materials and electrolytes issues, while Ca-ion batteries currently remain a curi-osity. Metal–air technologies, based on unlimited O2, have greatly benefited from progress in materials science and in analytical tech-niques. However, owing to their electrochemical chemical complex-ity, many challenges remain to be solved if these technologies are to make a significant impact on the future energy-storage landscape. The horizon is brighter for Li–S, but a common issue inherent to both Li–O2 and Li–S technologies is the need to protect or ideally replace the negative Li metal electrode

n terms of sustainability, rechargeable aqueous Na-ion tech-nology is attractive. But cost expectations have yet to be realized, raising the question of whether aqueous systems can ever be made cheaper than non-aqueous systems

Future batteries could have, in addition to the positive/negative out-puts, an extra analyser output

an we draw inspiration from the medical field and all the tool-ing that is currently used during surgery or in implants, and from the increased use of sensors in advanced manufacturing?

Possible future integration scenario for battery management.

Operando neutron diffraction and tomography studies on ‘real-world’ (18650) batteries under realistic cycling conditions have recently allowed the visualization of Li concentration gradients across the battery, providing insight on electrode failures, degrada-tion mechanisms and diffusion kinetics

. Grid and transport demonstration projects and bat-tery tests are already in progress to link traditional electrochemi-cal responses (such as current, voltage and impedance) with test routines appropriate to the technology and produce the ‘big data’ needed to extract new correlations and, ultimately, predict future performance.

Another burning question concerns the visualization of electron transfer and redox processes at even shorter length scales. The study of nucleation/growth kinetics of phases containing peroxide-like species by EPR imaging in the layered lithium-rich oxides is a first step, even though the resolution has been limited to micrometres.

The challenge is significant, but, given the critical role of these pro-cesses in battery cycle and calendar life, attempts to develop new tools to attack this issue must be worth the risk.

Trends towards sustainability for today’s batteries

Examples of operando techniques.

Many of these techniques have provided considerable insight into electrolyte and electrode degrada-tion.

The move away from the traditional and well-understood battery chemistries to more complex redox processes such as alloying and conversion, and the need to optimize more established chemis-tries, has motivated the development of new analytical operandotechniques that allow study of the fundamental mechanisms by which these materials operate, together with the kinetics of these processes

The Zn–air battery represents another potentially sustainable technology, but it has been challenging to develop a rechargeable cell, owing to side reactions such as carbonization and the for-mation of Zn dendrites.

Although the use of a non-aqueous-based electrolyte pushes up the cost, this finding has opened new avenues for explora-tion83, including the use of inorganic86 or organic inks87 in aqueous systems, with potential cost and energy-density advantages for grid-scale storage.

New approaches are sorely needed. Cheaper separators must also be developed84, and concepts such as membrane-free separators must be pursued.

Sustainability and cost have driven work on aqueous Li–O2 and Li–S systems, being aided by Visco’s pioneering work on the devel-opment of protected Li-anodes together with a ceramic membrane separator to obtain a two-compartment cell.

The Li–S system has been recently revisited as part of the quest for new sustainable storage technologies

But Li–S batteries were never commercialized, owing to severe hur-dles

challenges such as cathode/electrolyte stability and air handling remain to be tackled. It is still unknown whether a commercial cell can be developed. Recent results have demon-strated that reversible cycling by means of discharge products other than Li2O2, such as LiOH (ref. 66), LiO2 (ref. 67) and Li2CO3 (ref. 68) is also possible, with suitable redox mediators or catalysts.

Although the addition of LiNO3 helps to protect the Li anode64,65, either the generally ignored problem of the Li metal anode must be solved or it must be replaced by another (Li-containing) anode if practical batteries are to be developed.

They demonstrate that Li–air does not necessarily mean a low-rate, low-capacity battery, contrary to earlier views.

LiFePO4 is, in practice, no cheaper than the less environmentally friendly Co- and Ni-containing phase of formula LiNi1/3Mn1/3Co1/3O2, termed NMC

The use of more complex anions such as pyrophosphates (P2O7)4–,borosilicates, borophosphates and carbonophosphates17 is not competitive performance-wise, owing to the weight penalty associated with the heavier polyanions.

Gravimetric and volumetric capacities for the more abundant elements Mg and Ca (Fig.  1) are significantly higher than that of graphite. But making batteries from these elements is far from being a practical reality

However, the unrealistic expecta-tions of quick commercialization have diminished, as the early cells exhibited rapid capacity fade, large overpotentials, particularly on charging, and poor rate performance

Metal–air batteries have a theoretical energy density exceeding that of Li-ion batteries and the posibility of using unlimited fuel O2 as the posi-tive electrode.

Research into Na-ion technology is now accelerating, progress being rapid because of the many similar-ities of Li-ion and Na-ion chemistry

Replacing Li by more abundant metals Na, Mg and Ca.

Si, has received considerable attention, because its capacity is 10 times that of carbon. But the Li-alloying reactions (LixSi, where x ≤ 3.75) are accompanied by extremely large volume changes, owing to the large amount of inserted Li

Although some of these (with schematics shown in Fig. 2) are in the very early stages of commercialization, there is no clear-cut winner; several advances have, however, been made, and so optimism must prevail, motivating continued research and development of all of these technologies

The continued push for cheaper, higher-energy-density and more sustainable battery technology has led to a blossoming of research activities centred on new chemistries such as Na-ion, metal–air (Li, Na, Zn), Li–S, multivalent ions and redox flow, to name but a few.

Lithium-rich NMC phases with high Mn contents and extremely high capacities (>280  mAh  g–1) have been discovered

But these advances do not address concerns about lim-ited Li reserves, which result from the predicted increased battery demands

Renewable organic electrodes based on redox-active molecules containing electrochemically active C=O functions, such as the oxo-carbons Li2+xC6O6,which can be synthesized via ‘green chemistry’ from natural organic sources, represent one approach to developing greener Li-ion batteries

The LiFePO4 ‘success’ story has triggered extensive research on Fe-based polyanionic compounds including the silicates (Li2FeSiO4) (ref. 14) and borates (LiFeBO3)

Past efforts devoted to developing positive electrode materials with minimum ecological footprint have been rewarded by the develop-ment and commercialization of Fe-based polyanionic compounds, most notably olivine LiFePO4

Although progress has been encouraging, it is certainly not sufficient to meet our planet’s growing demands: we must push the frontiers faster and further in the years to come.

An operandomeasurement usually refers to a measurement made while the battery is operating (cycling), while the more general in situ term (mean-ing on-site) may refer to the measurement of a particular variable against a parameter relevant to the system, which could be time but could also be temperature, pressure or other parameters.

This concern has driven researchers to explore new, potentially more sustainable chemis-tries, including Na-ion, metal–air chemistries Li(Na)–O2, Li–S, multivalent (Mg, Ca), redox flow batteries (RFBs) and aqueous-based technologies,

These reserves are indeed limited, but Li can be recycled by hydrometallurgy, although the economics of such a process has yet to be worked out

they have revealed that today’s battery assembly process, including materials and recycling, is not as sustainable as generally thought, 400 kWh of energy being required to make batteries that deliver 1 kWh of energy, while releasing 75 kg of CO2

can we increase battery sustain-ability, while lowering cost and improving battery performance?

the production of Li-ion batter-ies should expand hugely over the years to come, hence reviving the issue of finite Li reserves.

consider the elemental abundance of any new materials or electrolytes, motivating work on, for exam-ple, Fe-, Mn- and S-containing cathodes and electroactive organic molecules.

The material fabrication step is by far the most problematic,

Although estimates vary widely, the predicted penetration of lithium-ion technology into these large-volume markets could result in as much as a threefold increase of production for the cathode material, reaching nearly 400,000 tonnes per year by 2020

the electrification of transport requires much cheaper and longer-lasting batteries.

Sustainability and cost concerns require that we greatly increase the battery lifetime and consider second lives for batteries.

we must integrate sustainability of battery materials into our research endeavours, choosing chemistries that have a minimum footprint in nature and that are more readily recycled or integrated into a full circular economy.

implica el consumo de grandes cantidades de agua, así como el riesgo de salinización de las capas de agua dulce

Si bien la minería del Li no es una minería a cielo abierto y el material explotado no genera liberación efluentes tóxicos al medio, toda actividad humana genera un impacto en ambiente.

En primer lugar es importante desmitificar el litio como una energía “verde”. El litio no genera energía, sino que la conserva. Como el petróleo, el litio es una fuente de recursos no renovables.

La demanda de Litio

Esta situación seguramente irá cambiando a medida que aumente la demanda global y el precio del litio (incentivando la exploración en lugares de mayor dificultad), pero por ahora la búsqueda de litio se focaliza en los lugares donde es más barato de extraer

El litio actualmente tiene numerosos usos en la industria y en la medicina1, sin embargo la mayor demanda de este mineral en los próximos años, según analistas internacionales, será para la fabricación de baterías de teléfonos inteligentes, tablets y, principalmente, autos eléctricos.

El Litio, según los más aventurados reportes de analistas económicos, ocupará en los próximos 8 a 10 años un rol esencial como elemento conservador de la energía.

El elevado consumo de agua para la obtención de litio vía evaporación es el impacto ambiental más significativo de esta actividad, que a diferencia de la minería a cielo abierto no utiliza explosivos ni libera efluentes tóxicos

la producción de baterías ion-litio8para lacreciente industria de la electrónica portátil (telefonía celular, reproductores de audio, computadoras),incentivó nuevasinvestigaciones destinadas a optimizar su funcionamiento, orientando a las empresas automotrices a optar por esta tecnología en la carrera por el desarrollo de los futuros vehículos eléctricos

Utilizando litio en la producción de materiales de electrodo, estas investigaciones posibilitaron el desarrollo de una nueva generación de baterías eléctricas, desechables y recargables.

el desarrollo tecnológico de acumuladores electroquímicos de litiopodría orientarse a satisfacer una parte importante de la demanda energética de la sociedad, a partir de la generación de energías renovables y sistemas de almacenamiento eficiente.

De ellas se precipita el litio bajo diversas formas químicas (generalmente carbonato de litio), utilizado en la producción de grasas, lubricantes, aluminios, medicamentos, aire-acondicionados y –lo más importante-baterías para la electrónica portátil y los vehículos eléctricos

se requiere de una tecnología limpia, de altocosto

Dada su baja adsorción, el litio puede lixiviarsefácilmente a los mantos acuíferos, por lo que se haencontrado en pequeñas cantidades en diferentesespecies de peces.

Los síntomas por intoxicaciones agudas de litioson fallas respiratorias, depresión del miocardio, ede-ma pulmonar y estupor profundo.

e han generado aproximada-mente unas 77 toneladas de este elemento por el uso ydesecho de baterías (véase cuadro 10)

Este tipo de baterías presenta la ventaja de redu-cir de 100 a 300 veces o más el volumen generado depilas desechables o primarias, sin embargo, algunosde sus componentes son más tóxicos

se convierten en residuos, sepuede calcular, durante los últimos siete años, unpromedio de 35,500 toneladas anuales. Esta cifra com-prende las baterías primarias (véanse cuadros 3, 5 y8) así como las secundarias de Ni-Cd, Ni-MH

una vez que cumplen sucometido de generar energía y son desechadas, loscompuestos a que dan origen en el medio ambienteson diferentes