Since the emergence of the Tzenkethi and the mystery surrounding their fervent crusade, they have continued to exhibit design and tactic ingenuity the like of which the Alliance has yet to see. It is been in the best interest of the Alliance to continue pursuing new technologies as new dangers present themselves. The Tzenkethi harness shield power and distribution effortlessly. Their battle tactics indicated an admirable reliance on one another. This collectivism has allowed their technology to have situational strengths at the cost of weaknesses that can be offset while in larger groups.
The tireless efforts of the Alliance have now come to fruition. Tzenkethi design principles have been applied to construct new starships and technology to outfit our captains with. These captains will be able to experience the shielding superiority and tactical mobility of a Tzenkethi ship. Captains can also equip themselves with Diffusive Tetryon armaments to increase their shield optimization options. And, for those ambitious enough, genetic modifications are available to address Tzenkethi physicality and munitions that couldn’t be replicated with simple fabrication.
For Star Trek Online this lockbox includes a major influx of updated capabilities in the fields of shielding and maneuverability. Every piece is uniquely Tzenkethi, focusing on situational strengths and defenses. With this lockbox we have also included some enjoyable surprises. Such as…
- A Lukari N’kaam Scout Ship [T5], discussed in further detail below.
- A Vanity-Only Tzenkethi Shield, capable of dropping from the Weapon pack. This marks the first time we’ve released a shield for the sole purpose of bringing the visual identity of a group to the players.
- For the first time ever, a Lobi Store, Tzenkethi Ground Set. Inspired by Tzenkethi design in both mechanics and visuals!
- A Tetryon Energy Torpedo in the Tzenkethi Lobi Store Space Set!
To begin, the Tzenkethi Lock Box’s Grand Prize is the Tzenkethi Shuk-din Escort [T6], and as expected with Tzenkethi design, this ship is highly maneuverable with immense shielding capabilities for its size.
Coming equipped on the Shuk-din Escort is the Console – Universal – Peripheral Refraction Array. This console represents the current pinnacle of Tzenkethi shield technology, allowing the starship to massively increase their defensive capabilities along all non-Forward shield facings. The forward array is instead tuned to offense, increasing the damage dealt by the starship's weaponry against any foe within their forward-facing 90-degree arc.
Additionally the Shuk-din Escort is fitted with the latest experimental weaponry option, the Protomatter-Laced Sheller. Based on an original Tzenkethi design, the protomatter-laced payload it delivers is split between Kinetic and Radiation damage, and the damage it deals is increased against foes the closer they are to being directly in front of your ship. This weapon is capable of being fitted into any starship with an Experimental Weapon slot.
Completing the Starship Mastery Path on the Tzenkethi Shuk-din Escort [T6] unlocks access to the following starship trait:
- Using any Shield Healing Bridge Officer Ability will cause foes near the healed ally (or self) to suffer an amount of Shield Drain proportionate to the amount of shields restored.
In a welcomed show of continued support the Lukari have contributed to this endeavor as well. Captains will be able to have a chance at winning a Lukari N’kaam Scout Ship [T5]. In the process of making the more state-of-the-art Ho'kuun vessel, the Lukari also experimented with smaller, lighter spacecraft. The N'kaam represents some of those earlier engineering explorations, and although not quite as impressive as it's big sisters, is still quite capable in its own right. Players who acquire this ship will be able to use its ship costume on the Lukari Ho’kuun [T6] as well.
Scout Ships are a unique combination of Science Vessel capabilities, in a much smaller, faster and more fragile package. They come with built-in Sensor Analysis and Subsystem Targeting, as well as a Secondary Deflector slot, and are able to benefit from Raider Flanking bonuses as well. These nimble vessels are also similar to a Raider in that they boast an abundance of universal bridge officer seats, can load dual cannons, and have similar weapon slot configurations.
As part of a deal with the Ferengi for their support in technological advancements, a Captain will be able to purchase the Tzenkethi Rhas’bej Battlecruiser [T6] from the Lobi Store.
The Rhas’bej Battlecruiser comes equipped with the Console – Universal – Momentum Manipulator. The inner workings of this technology are still a bit of a mystery, but it is said to replicate and redirect both kinetic and potential energy, in order to alter fundamental aspects of physics. Regardless of how it works, it has proven to be an effective weapon of choice for the Tzenkethi, allowing even their larger warships to suddenly execute maneuvers otherwise assumed impossible, while simultaneously boosting their weapons' destructive capabilities.
This console also provides a passive boost to Radiation, Kinetic and Physical Resistance Rating, and Outgoing Shield Healing.
Completing the Starship Mastery Path on the Tzenkethi Rhas’bej Battlecruiser [T6] unlocks access to the following starship trait:
- Every 2 sec, while below 25% throttle, you gain increased Shield Capacity, Shield Hardness and Turn Rate.
(Additional information on the above starships will be contained in a separate Developer Blog.)
A special console based entirely on tried and true Tzenkethi strategies can also be acquired from the Tzenkethi Lock Box: The Console - Universal - Shared Processing Integration. Derived from the salvaged technology of their Broln’ta Cruisers, this console allows the user to activate a repair device that will heal the hulls of nearby allies, including the users, while simultaneously raising damage resistance. The effectiveness of the device depends on their distance from the user. This is largely due in part because of the nature of the technology. It uses both individuals’ power to more efficiently process repair protocols.
Space Weapons and Vanity Shield
The Tzenkethi Lock Box will also feature new Space weapons within the Diffusive Tetryon Weapons Pack. This box contains Diffusive Tetryon versions of all standard space weapon types. Additionally the weapon pack will have a chance to drop an Omni-Directional Diffusive Tetryon Beam Array or Wide-Arc Diffusive Tetryon Dual Heavy Cannons. That’s not all though, lucky captains will also be able to receive a Tzenkethi Vanity Shield from this pack. This vanity shield can be equipped in a ship’s vanity shield slot to gain the visual look of a Tzenkethi starship.
All Diffusive Tetryon weapons have a chance to apply:
- to target: -10% Shield Resistance for 10 sec
- to self: +10% Shield Resistance for 10 sec
(Refreshes duration when re-applied)
New Personal Traits are also available within the Tzenkethi Lock Box. They are universal and available to all species.
- Ground: Indirect Shielding
- +All Damage Resistance Rating based on shield percent remaining.
- Ground: Permeating Radiation
- Your Outgoing Radiation Damage additionally slows the target’s run speed for a short duration.
- Ground: Tumultuous
- While Threatening Posture is active, the chance to gain stacks of Max Hitpoints is doubled, as is the rate at which they can be gained. While Threatening Posture is not active, your threat is reduced by an additional 50%.
- Space: Oblique Shielding
- +All Damage Resistance Rating based on shield percent remaining.
- Space: Galvanized Munitions
- A percentage of your outgoing Cannon damage is returned as healing to your forward shield facing.
- Space: Menacing
- While Threatening Stance is active, the chance to gain stacks of increased Max Hull is doubled, as is the rate at which they can be gained. While Threatening Stance is not active, your threat is reduced by an additional 50%.
Captains may also find Tzenkethi Kit Module packs. These Kit Modules are universal, and can be used by any class.
Creates a shockwave that deals Kinetic Damage, knocks up, and slows enemies. In addition, it leaves a debuff that reduces the target’s damage resistance rating vs melee attacks for a short duration.
- Protomatter Munition Deployment
Launches five delayed protomatter strikes on the target. Each strike deals Kinetic Damage and leaves a hazard that deals Radiation Damage.
Creates a fixed position point of volatile artificial gravity. This pulls in enemies and cripples their offensive, defensive, and mobility capabilities for a short duration.
Duty Officer Assignments
Captains who wish to delve further into the behind the scenes intelligence operations involving the Tzenkethi can do so in the Tzenkethi Intelligence Duty Officer Assignments. Each of these five assignments yields high XP and Dilithium rewards. Completing all the assignments gives additional Dilithium ore and a Title!
Lobi Store Ground Set
For the first time ever, the Lobi Store will be receiving a ground set themed around the Tzenkethi, TheVranh’ko Quintessence.
Tzenkethi Retrofit Assault Cannon
This two-handed assault weapon is a retrofit design from one of the powerful one-handed Tzenkethi gauntlet weapons. Infused with protomatter technology, this tetryon weapon is capable of dealing sustained punishing damage. The primary fire is a fast firing flurry of tetryon bolts. While the secondary is a torrent of continual shots that increase in damage the longer the toggle is active. Consequently the strength it requires to sustain this onslaught also means that the user is increasingly slowed while the toggle is active as well.
Tzenkethi Personal Shield
This Personal Shield uses Tzenkethi shield technology to bolster its capacity to new heights. It also comes equipped with the ability to heavily strengthen flank angles in dire situations.
When taking damage while shields are below 50%:
- +50% Shield Resistance for 10 sec
- +80 Bonus All Damage Resistance Rating to damage from behind for 10 sec
(Only applies once per 30 sec)
Tzenkethi Retrofit Armor
The Tzenkethi Retrofit Armor was made by scientists to replicate the fortitude and power of Tzenkethi personal armaments. The major hurdle was miniaturizing the Tzenkethi features to fit a more versatile selection of species. This armor also comes equipped with kinematic pneumatic actuators, which imbue the user with increased physical capabilities for a short period of time.
Charge the enemy and apply:
- Physical Damage
- 60% chance: Knockback 6 feet
- To self: +50% Melee Physical Damage for 10 sec
Vranh’ko Quintessence Set Bonuses:
Set 2: External Circuit Integration
- +20% Shield Resistance
- +25 Kit Performance
Set 3: Overwhelming Capacitors
- +25% Tetryon Damage
- +30% Maximum Shield Capacity
Lobi Store Space Set
The Lobi Store also has a new set of Space equipment available for purchase, The Tzenkethi Resolve.
Advanced Diffusive Tetryon Torpedo Launcher
This Torpedo launcher fires projectiles that deal heavy Tetryon damage. Advanced Diffusive Tetryon projectiles deal average damage and have a longer than normal recharge. Unlike most torpedo launchers, the Advanced Diffusive Tetryon Torpedo Launcher's damage is enhanced by abilities and items that improve Tetryon damage, and not those that improve traditional Torpedo weapons.
Advanced Diffusive Tetryon Energy Weapon (Dual Beam Bank or Dual Heavy Cannon)
These narrow arc energy weapons deal potent Tetryon damage with a chance to trigger radiation damage as well as the standard Diffusive Tetryon proc.
Console - Universal - Biased Configuration Modulator
Tzenkethi designs might be unconventional but they have proven to be effective. This console follows the designs of biased configurations, allowing the user to increase their damage in their forward firing arc above all else.
Tzenkethi Resolve Set Bonuses:
Set 2: Motivational Measures
- +25% Projectile Damage
- +15% Shield Resistance
Set 3: Subatomic Aptitude
- +25% Tetryon Damage
- Activating a Torpedo Bridge Officer ability applies:
- +25% Flight Turn Rate for 5 sec
There are many other prizes within the Tzenkethi Lock Box for players to acquire, such as R&D Packs, Boosts, and other assorted items.
The Tzenkethi Lock Box, as well as the additional Lobi Store entries, will be coming to Xbox One and Playstation 4 with the Season 14 release.
Matthew “CulturedSoup” Campbell
Star Trek Online
sto-xbox, sto-playstation, star-trek-online,
The invention relates to a method for hydrometallurgical treatment of cells and batteries comprising at least a lithium-based anode, a salt dissolved in an electrolyte and a cathode comprising at least one metal or a combination of metals selected from cobalt, nickel, manganese and iron, for recovering the recoverable fractions.
The increase in portable electronic products has resulted in an expansion of the cells market (30 billion dollars in 1998) with an annual growth of 6% and the autonomy requirements via sources having a good energy density have doped the portable batteries market which presents an even greater growth (12%). In particular, lithium systems have made considerable progress over the last few years (plus 45% in 3 years).
At the present time, batteries called ion lithium batteries and polymer electrolyte batteries are the major technological innovation of the last fifty years in the electrochemical generator field. However, despite the numerous advantages related to performances, lithium systems continue to constitute a large source of products having a recognized environmental impact. The effects are mainly related to the following components:
- heavy metals such as cathodic materials,
- conducting salts with a fluorine, arsenic or sulfonated compound base
- organic solvents and
- a very reactive alkaline metal.
Many of these elements are not degradable and often present a high degree of toxicity either directly as regards the health of human beings and animals or indirectly by polluting the soil, water, plants and food chain. Even disseminated in waste, they contribute to polluting larger matrices or to accentuating already problematic situations in the case of incineration with household waste. Moreover, dispersing metals in waste is in contradiction with preservation of natural resources. Furthermore, some of the metals used in lithium systems are difficult and expensive to extract.
The state of the art shows a large number of attempts to make proposals for treating lithium systems. Thus, the U.S. Pat. No. 6,511,639 describes a method for recovering negative electrodes by means of a thermal treatment and only concerns lithium ion batteries. In the document WO-A-0223651, the treatment associates a cryogenic step followed by an incineration step and only concerns vanadium oxide-based polymer lithium batteries.
The method described in French Patent application FR-A-2812973 proposes wet crushing of lithium ion batteries and nickel metal hydride batteries whereas the method described in the document JP-A-11185833 proposes a solution based on a thermal treatment and only concerns lithium ion batteries. The method according to the Patent application WO-A-9934473 proposes extraction using acetonitrile and only concerns lithium ion batteries.
The method according to the U.S. Pat. No. 5,882,811 proposes cutting with a water jet followed by electrolysis in molten LiCl medium and distillation of the electrolyte. It only concerns lithium ion batteries as does the method according to the Patent application JP-A-10330855 which proposes direct thermal treatment in a rotary furnace.
The method according to the Patent application JP 10287864 proposes extraction by solvent and only relates to lithium ion batteries. The methods according to the Patent applications JP 10046266, JP 10158751 and JP-A-10074539 propose a thermal treatment comprised between 350° C. and 1000° C. and only concern lithium ion batteries.
On the other hand, the only methods industrially implemented in the world are two in number:
1—The method called TOXCO proposed in the U.S. Pat. No. 5,888,463 and presented by W J. McLaughlin, Lithium battery recycling Proceedings of the 5th International Seminar on Battery Waste Management (Florida 1993). It is applied in the United States for recycling batteries and cells made of lithium in a mixture (LiSO2, LiSOCl2, LiMnO2, LiFeS2, Li-ion and LiCFx). The batteries and cells are frozen in liquid nitrogen at −196° C. before being crushed. The homogenates are recovered in an alkaline solution to neutralize the acid compounds emitted (H2, SO2, SOC12 . . . ) and to hydrolyze the organic solvents. The lithium salts formed (Li2SO4, LiCl) are separated from the residual metallic and plastic fragments by a screening operation. Adding sodium carbonate to the solutions enables the lithium to be precipitated in carbonate form before purification and recrystallization of a technical quality salt. No indication is given on recovery of the cathodic metals.
2—The SONY-SUMITOMO method presented during the 5th International Seminar on used battery and cell management (Florida USA, October 1998). It is applied in Japan only on Li-ion batteries. The method is based on calcination at a temperature of about 1000° C. in a furnace. After calcination, the residues are crushed and screened. The screened powder contains cobalt oxides and other oxides. No lithium recycling indication is given.
In a general manner, it can be observed from the state of the art that:
- Thermal methods give rise to large problems of gas emissions in particular of greenhouse effect gases and are in contradiction with the commitments of the states that signed the recent international agreements.
- Wet channel crushing processes give rise to large safety problems as regards the hydrogen emitted when the batteries are crushed. This problem also arises in relation with any method proposing a mixture of lithium batteries and aqueous system.
- The use of acetonitrile gives rise to large safety problems in particular for the operating personnel and for emissions in the natural environment.
And finally, two major handicaps are ascertained among all the proposed methods:
1—Among 11 proposed methods, only one method is designed to treat all types of lithium batteries,
2—Two methods out of the 11 are used industrially to date.
Lastly, in non-thermal methods, no precise and safe solution is proposed for management of opening of the batteries.
The object of the invention is to provide a treatment method enabling the shortcomings of the prior art to be remedied and, more particularly, providing a framework for performing recycling of lithium systems without any pollution transfer with a maximum recovery ensuring conversion of the resource into added-value compounds.
According to the invention, this object is achieved by the appended claims. More particularly, this object is achieved by the fact that the method comprises dry crushing at room temperature in an inert atmosphere, treatment by at least magnetic separation and densimetric table followed by aqueous hydrolysis to recover at least the lithium in carbonate or lithiophosphate form, an anion of said electrolyte salt and a concentrate comprising at least one metal of said cathode.
To overcome the different shortcomings set out above, the present invention relates to a method for treating all lithium systems separately or mixed. To perform recycling of batteries for beneficiation purposes, it is important to open the system by crushing the batteries to access the recyclable fractions. However, a lot of batteries to be recycled still have a strong charge and crushing them produces sparks and large inflammations or even explosions in particular with SO2 or SOCl2 systems. To avoid these two drawbacks, two complementary solutions are implemented in the present invention.
Crushing is made safe by means of inert gases in very economical manner by placing the crushing system in an enclosure with a controlled atmosphere and pressure and by using suitable crushing systems.
In a first embodiment of the invention, the crushing operation is performed beforehand by shredding by means of a rotary shearing machine with a low speed of rotation preferably less than 11 revolutions per minute (rpm). This step is designed to release the internal stresses of the batteries. In a second step, the shredded charge is crushed in a rotor system rotating at a mean speed preferably lower than 90 rpm.
In a second embodiment of the present invention, the two crushing systems are placed in a tightly sealed enclosure made inert by means of a gas that is either argon, or carbon dioxide, or a suitable mixture of the two gases. Examination of the densities of the gases show that argon and carbon dioxide will provide a good protection above the crushed charge.
These two gases will expel the oxygen and nitrogen and provide a gas covering above the mill blades and above the crushed batteries. In addition, the presence of carbon dioxide will result in initiating passivation of the metallic lithium by formation of lithium carbonate at the surface, which slows down the reactivity of this metal.
In the case of a mixture of these two gases, the proportion varies from 10% to 90% of argon and from 90% to 10% of carbon dioxide, but the proportion of argon in the mixture is advantageously comprised between 10% and 35%.
Gas injection is controlled by the residual oxygen content and by the internal pressure. These two parameters are advantageously set at:
1—an oxygen content comprised between 100 and 10000 ppm but preferably close to 5000 ppm,
2—a differential pressure comprised between 30 and 130 millibars but preferably close to 80 millibars.
Injection of inert gas is preferably only performed if one of the two parameters exceeds the setpoint values which enables the setpoint value of the consumptions to be considerably reduced.
The crushed charge is then sent to a vibrating screen with a mesh size smaller than or equal to 3 mm and equipped with a high-induction magnetic separator at the end of its output and with a densimetric table. This operation enables 4 fractions to be obtained in a single run:
1—the undersized fine fraction which is rich in metal oxides and carbon,
2—the magnetic fraction which is composed of stainless steel from the casings of the cells and batteries,
3—the dense non-magnetic fraction which is composed of non-ferrous metals and
4—the non-magnetic fraction with a low density and which is composed of a mixture of paper and plastic.
Only the undersized fine charge, obtained at 1 and composed of metal oxides and carbon, has to be subjected to subsequent treatment. This treatment begins by screening at 500 micrometers which enables an undersized fraction rich in cobalt and poor in copper (<0.3%) to be obtained. This charge can then be a material treated by any recycling method of metal oxides, in particular those having a base comprising cobalt, nickel and manganese or any mixture of these three metals.
In a particular embodiment of the present invention, the undersized fine charge that passes the screening is suspended in heavily stirred water. This turbulence in the bath enables the metal and lithium oxides to be released. Mixing the lithium hydroxide in solution will alkalize the solution up to a pH of more than 12.
Hydrolysis of the crushed charge leads to the formation of hydrogen. However, management of the addition rate of the charges in the leaching reactor and creation of a very strong turbulence above the bath prevent risks of inflammation of the hydrogen and of explosion. This operation is associated with making the atmosphere above the bath poorer in oxygen. This air comes from the suction of the mill casing and enables an oxygen-poor atmosphere to be maintained so as to permanently be at a concentration of less than 0.5% in volume, which is situated in the safety range of hydrogen. At the end of the hydrolysis reaction and after filtration, an alkaline solution of lithium salts and a suspension of metal oxides and of carbon are obtained.
The solution is then treated so as to separate the dissolved lithium whereas the insoluble charge is treated to recover the cathodic metals. Recovery of the dissolved lithium is performed from a solution having a pH close to 12. Acidification by means of a suitable reactant enables the lithium salt to be precipitated.
In a particular application of the present invention, the lithium is precipitated in the form of carbonate and the gases output from the mill are used as carbon dioxide input as precipitation reactant. This particular embodiment of the invention is advantageously applicable in the case of recycling of a mixture of cells and batteries including thionyl chloride systems. This advantage is obtained by means of the different solubility of the three gases in water at room temperature and at ambient pressure.
Precipitation is performed by adjusting the pH from its initial value close to 13 to a value of 9. The precipitated product is washed by carbon dioxide-saturated water then dried at 105° C. On account of the solubility of Li2CO3, the residual lithium concentration remains high, about 1.8 g/l, and requires subsequent treatment.
In another application mode, the leaching solution having a pH of 12.1 and containing 11 g/l of lithium is neutralized by means of phosphoric acid at 85% to a pH of less than 8.5. The solution is then realkalized up to a pH of more than 12. The precipitate formed is then separated by filtration. The residual lithium concentration is 89 mg/l meaning that an extraction ratio of more than 99.15% is achieved. This residual lithium concentration is a limit concentration as it corresponds to the solubility of Li3PO4 which is 400 mg/l (Hand Book of Chemistry and Physics, D. L. Lide editor, 75th edition, 1993, monograph of chemistry and physics).
The precipitated solid is dried and then analyzed by X-ray diffraction and by chemical analysis. The Li3PO4 content is 93% and analysis by X-ray diffraction shows that the product is a hydrated lithiophosphate with a ½ water molecule and therefore a water content of 7%. This strongly confirms the purity of the product obtained as shown by the X-ray diffraction spectrum presented in
The washed charge is treated differently depending on its composition. As thionyl chloride cells have very little influence on the contribution of cathodic materials, the different charges will be differentiated according to the manganese/cobalt ratio.
Three cases are encountered during treatment of mixed lithium cells and batteries.
In case No1, on account of its manganese composition, the fine charge composed of oxides and carbon is usable in all the methods described in the state of the art and in particular in the two methods respectively described in the Patent applications FR-A-2704098 and EP-A-0620607 and in the Patent applications FR-A-2827710 and WO-A-03021708.
In case No2, the charge is dissolved in a 2N sulphuric medium at 80° C. in the presence of steel shot in an iron/cathodic mass ratio of 0.15. The pulp obtained is cooled down to 60° C. and then filtered. The solid part contains the carbon whereas the solution, which is at a pH of less than 3, contains zinc sulphate and manganese as well as other metallic impurities, in particular copper. The copper is cemented by means of steel shot. After cementation, divided metallic copper and a solution with a pH comprised between 2 and 2.85 are obtained. This pH is raised to a value of 3.85 by means of soda at 20%. This modification of the pH results in precipitation of the iron in the form of hydroxides. This purified solution is then neutralized at pH 5.8 and then subjected to electrolysis to obtain metallic cobalt in a traditional single-compartment electrolysis configuration. In particular, a previous treatment of the Applicant on zinc and manganese sulphate solutions as described in the Patent applications FR-A-2827710 and WO-A-03021708 can advantageously be used.
In the case of the present invention, electrolysis is performed at a temperature of 55° C. in a current density comprised between 400 and 600 A/m2 by using a stainless steel cathode and an antimony-lead alloy anode. The manganese precipitates in oxyhydroxide form and in dioxide form. After filtration and leaching, it is sent to the recycling channels known in the state of the art and in particular those already mentioned for case No1. The solution, which becomes poorer in cobalt and manganese, is richer in acid which is re-used at process input.
In case No3, the charge is mixed in solution and then purified in the same way as for case No2. The solution resulting from purification is then oxidized to a pH comprised between 2.3 and 2.8 by means of sodium hypochlorite to precipitate the cobalt hydroxide (III).
At the end of the treatment of cases 2 and 3, the solution contains a part of lithium salts resulting from reduction of the cobaltite or inserted in the MnO2 of the primary elements. This solution is neutralized by means of soda at a pH of 8.5 to recover all the metals still remaining in the solution, and is then sent to the leaching water treatment where it undergoes the same treatment to recover the lithium in lithiophosphate form.
The industrial implementation method in a continuous process was designed on the basis of pilot tests at a size of 10 kg/hour attesting to the operational and industrializable nature of the invention as set out in .
The following description deals with a method for applying the present invention to lithium-ion batteries without this having an exhaustive nature. The mechanical treatment 1 is performed in a tight chamber wherein two mills are arranged in series. After the chamber has been scavenged by means of a gas composed of 20% argon and 80% carbon dioxide, 10 kg of mixed cells and batteries are input in continuous manner via a double air-lock. The gases output from 1 are treated at 2 by leaching with water and neutralization by means of soda. The homogenate is extracted by means of an endless screw via a double air-lock. It then undergoes physical treatment 3 by means of a high-induction magnetic separation and a densimetric table. On completion of this treatment, the fine and dense charge is composed of lithium cobaltite, carbon and lithium carbonate as shown by the X-ray diffraction spectrum presented in . It is treated by leaching with water at 4 to recover the soluble lithium. After solid/liquid separation, the solution is sent for recovery of the lithium by precipitation at 5 whereas the solid fraction of cobaltite 6 is recyclable in metallurgy in processes where cobalt has to be added. The characteristics are:
To illustrate the feasibility of the whole method emanating from the present invention, the solid fraction 6 resulting from the treatment 5 is sent for acid leaching 7. After dissolution of the lithium cobaltite, the solution is filtered to separate the carbon and is then purified from the metals other than cobalt at 8. The cobalt sulphate and lithium solution 9 is then separated into two fractions. A first fraction is subjected to electrolysis 10. On completion of this electrolysis, cobalt cathodes are obtained and also a solution poor in cobalt sulphate and enriched in sulphuric acid 11 that is sent to leaching input. The second fraction is oxidized by means of sodium hypochlorite at 12 to obtain a trivalent cobalt hydroxide. The solution then no longer contains any lithium sulphate which is sent to 5 for precipitation of the lithium phosphate.
In this implementation, recycling of the lithium cobaltite is well proven in three different treatment channels (cobaltite as is, cobalt cathode and trivalent cobalt hydroxide). The three channels being illustrated as to their industrial feasibility, the choice will depend on the capacity of the installation and on the proximity of the recycling channels.
Extension to the Recovery of the PF6 Anion:
It is commonly recognized that the salt LiPF6 breaks down in water as follows:
This results in the PF6 anion disappearing and in gas being released above the aqueous solution. During our experiments, we ascertained that when treating mixed batteries and cells with a Li—SOCl2 and Li—MnO2 or Li-Ions base, no emission took place. This confirms the stability of LiPF6 in aqueous solution under our conditions. We then sought to confirm the presence of the PF6 anion by analysis. The hydrolysis solutions recovered at 4 () were analyzed by Nuclear Magnetic Resonance (NMR) using scanning at 188.3 MHz for fluorine 19 and at 81 MHz for phosphorus 31. It is known that phosphorus resonates in the form of a heptet and fluorine in the form of a doublet. The values of constants and the chemical displacements of 19F and 31P () enable the PF6 ion to be identified in an aqueous solution without any ambiguity. We deduced therefrom that one of the components provided by the chloride cells played the stabilizing role of the PF6 anion. These components are SO3, HCl, LiCl and AlCl3. Our complementary tests to study the stability of LiPF6 in the presence of these components showed that LiCl plays the role of stabilizer of LiPF6 in an aqueous solution.
As the PF6 anion is stable in our aqueous solutions, we looked for possible ways of recovering it. The state of the art did not show any known way for precipitating the PF6 ion in aqueous effluents. Studying the solubility of various PF6 salts led us to seek for a cation enabling the hexofluorophosphate ion to be quantitatively precipitated. This precipitation was conducted in an aqueous medium from our stabilized solutions. We directed our studies towards larger cations than the lithium cation. As the solutions are stabilized by the chloride anion, we tried the chlorides of alkaline cations such as ammonium. The solubilities obtained are:
It became apparent that the solubility depends, among other things, on the size of the cation as shown by the following table setting out the solubility versus the ionic radius:
The lowest solubilities are achieved with very onerous cations such as Cs and Rb, incompatible with an industrial application. The solubility achieved with the ammonium ion (0.43 M/L, i.e. 3.3 g/l) remains insufficient for quantitative recovery. We therefore had to direct our research towards larger cations. As the solubility obtained with the ammonium ion is however rather low, we then used quaternary ammonium salts of the R4N+ type (with R=methyl, ethyl and butyl). These products are extensively used, in particular in industrial manner and in particular as cationic surfactants in the detergent industry. The solubilities obtained are all lower than those obtained with the ammonium ion but remain higher than 8×10−3 M/l (i.e. 1.2 g/l). We then explored other larger cations and in particular those reputed to give relatively low solubilities with the perchlorate ion the configuration whereof is close to that of hexafluorophosphate. Better results than the previous ones were obtained with two cations which are:
- the hexamine complex of nickel: [Ni(NH3)6]2+
- and dihydro-1,4-diphenyl-3,5-phenylimino-1,2,4-triazole (Merck Index No12,6711):
The solubilities obtained at room temperature are s<200 mg/l for the hexamine complex of nickel and s<20 mg/l for the Dihydro-1,4-diphenyl-3,5-phenylimino-1,2,4-triazole.
Extension to Recovery of New Lithium Iron Phosphate-Based Cathodic Materials.
The cathodes of lithium-ion batteries marketed at present are lithium cobaltite base. However, the cost and toxicity of cobalt on the one hand and the safety problems that may result from the use of cobaltite on the other hand have led to large research efforts being made to develop new cathodic materials. According to the state of the art, the most promising material seems to be lithium iron phosphate (LiFePO4). We synthesized lithium iron phosphate according to A. Yamda et al. Journal of Electrochemical Society, volume 148 No3 pA224 (2001). Then we proceeded to treat this compound as a cathodic mass 6 resulting from the physical-chemical treatment as described in .
The material is placed in solution in a 2N sulphuric medium at 80° C. in the presence of steel shot with an iron/cathodic mass ratio of 0.15. The solution obtained is cooled to 60° C. and then oxidized by means of 30% volume hydrogenated peroxide at pH 3.85. The iron is then separated in the form of oxyhydroxide of the ghoetite type. The lithium solution is then treated according to the method described in 5 in FIG. 3/5. By this method of implementation, the iron, lithium and phosphate of the cathodic material are recovered. By this method of implementation, the method remains applicable when modifications take place in the composition of lithium batteries with a change in the cathodic composition.