I need Si not SiO2 for Lithium to bond to in the anode, ball milling with aluminum and then heating to 350 degrees celcius should allow a reduction of silica to silicon.

http://scitation.aip.org/content/aip/journal/jap/80/11/10.1063/1.363669

This paper describes the failure of diodes made with Al SiO2 Si do to high temperature.

Going forward I need a few more materials to make these things work as they should.

Lithium-Sulfur-Silicon Battery

I should receive some commercial poly-propylene semi permeable lithium ion battery seperator in the mail anyday from china.

The electrolyte is the most debated section of these batteries in the literature. I have attempted solid electrolytes this past week using PMMA to no success.

It seems going forward a liquid electrolyte will be the simplest way to demonstrate viability. Ultimately a solid sol-gel PEO electrolyte will be necessary but I need quite a bit of more equipment before I can process PEO.

1.0 Molar lithium b(TFMS) the standard in academia for electrolytes and prelithiation of the anode, costs around 60 dollars for 10 grams and should be immediately ruled out for commercial applications due to cost. This leaves me with using lithium perchlorate for pre lithiation of the anode and for the 1 molar solution in the electrolyte.

Using LiOH in the electrolyte was folly as it doesn't solvate well in PEG 400 but that was not indicated in any resource I could find.

Also using PEG 400 solely for the electrolyte will not work, instead I will probably be using a mixture of Tetrahydrofuran (THF) 1000Ml Composite Bottle Reagent Grade, 1,3-Dioxolane, =>98.0%, stabilized, Synthesis Reagent, 25mL, 1,2-Dimethoxyethane, =>99.0%, Analytical Reagent, 30mL. And for the lithium in the electrolyte .1 molar lithium nitrate, and 1 molar lithium perchlorate.

Pre lithiation can be achieved with lithium salts and silicon in a ball mill using hexane as a lubricant???? http://pubs.acs.org/doi/abs/10.1021/ic501923s I love staring at abstracts trying to make sense of things, I am hoping they didn't use Li b(TFMS) in this study and used something more like lithium perchlorate. It's worth a shot and I am going to try it as a step in between the, hydrothermal reduction of silicon dioxide and oxidized nano carbons into silicon carbide, and the final step of blending with the binder and applying to the charge carrier.

Artificial Muscle

I am starting to question if this is wholly feasible, I am on the edge of buying a 15% by weight igMWCNT to 85% PA 6/6 masterbatch from cheaptubes.com I know for a fact it will probably be too brittle but combining something more akin to 6% igMWCNT and 3% reduced graphene oxide would probably work better and retain more of pristine PA6/6's mechanical properties. However, cheaptubes really means cheap tubes and nothing else all their graphene is synthesized and is incredibly expensive. The resistivity of the 15% master batch is spot on with what I need for this to work at 2 ohms per cm. Mike at cheap tubes hasn't gotten back to me yet on the physical characteristics of these masterbatches. There is always the option of twisting these up warm, but I just don't have any of that figured out yet, this will work in some form or fashion it is not obvious, however.

Work continues on designing a water cooling system by 3d printing molds for molds I will have more on this later as I have already release too many defunct mold models.

Introduction

Here in lies the Blueprint for creating the ultimate Lithium Ion Sulfur Cathode Silicon Anode battery. It is amazing academia does all the scientific work with proper control but hardly ever combines the findings into one work. I will be updating this as I tweak my battery and fill in the blanks. Excerpts and licensing noted where required.

The Electrolyte

A switch to a poly sulfide shuttle is in order as very low decay is possible. The difficulty lies in keeping sulfur out of the anode as I will be using a silicon electrode. The loading of poly-sulfide in the electrolyte keeps sulfur in the cathode from migrating to the anode causing shorter life of the cell. I will be using calcium polysulfide.

http://www.sciencedirect.com/science/article/pii/S037877531301999X

Polysulfide shuttle control: Towards a lithium-sulfur battery with superior capacity performance up to 1000 cycles by matching the sulfur/electrolyte loading

Xin-Bing Cheng,Jia-Qi Huang,Hong-Jie Peng,Jing-Qi Nie,Xin-Yan Liu,Qiang Zhang,Fei Wei

Journal of Power Sources

Elsevier

1 May 2014

Copyright © 2013 Elsevier B.V. All rights reserved.

A manganese functionalized zeolite matrix will provide support for the Calcium Poly-sulfide as was used in this paper. The zeolite I will be using is naturally occurring and readily available.

http://www.sciencedirect.com/science/article/pii/S0378775314018035

Manganese modified zeolite silicalite-1 as polysulphide sorbent in lithium sulphur batteries

Vida Lapornik,Natasa Novak Tusar,Alenka Ristic,Rajesh Kumar Chellappan,Dominique Foix,Rémi Dedryvère,Miran Gaberscek,Robert Dominko

Journal of Power Sources

Elsevier

15 January 2015

The Anode

A Graphene oxide membrane will be utilized to keep poly-sulfides out of the anode as was demonstrated here. This will also reduce self discharge.

http://pubs.acs.org/doi/abs/10.1021/nn507178a

"Lithium–sulfur batteries hold great promise for serving as next generation high energy density batteries. However, the shuttle of polysulfide induces rapid capacity degradation and poor cycling stability of lithium–sulfur cells. Herein, we proposed a unique lithium–sulfur battery configuration with an ultrathin graphene oxide (GO) membrane for high stability. The oxygen electronegative atoms modified GO into a polar plane, and the carboxyl groups acted as ion-hopping sites of positively charged species (Li+) and rejected the transportation of negatively charged species (Sn2–) due to the electrostatic interactions. Such electrostatic repulsion and physical inhibition largely decreased the transference of polysulfides across the GO membrane in the lithium–sulfur system. Consequently, the GO membrane with highly tunable functionalization properties, high mechanical strength, low electric conductivity, and facile fabrication procedure is an effective permselective separator system in lithium–sulfur batteries."

Permselective Graphene Oxide Membrane for Highly Stable and Anti-Self-Discharge Lithium–Sulfur Batteries

Jia-Qi Huang†, Ting-Zhou Zhuang†, Qiang Zhang*†, Hong-Jie Peng†, Cheng-Meng Chen‡, and Fei Wei†

† Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

‡ Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China

ACS Nano, 2015, 9 (3), pp 3002–3011

DOI: 10.1021/nn507178a

Publication Date (Web): February 18, 2015

Copyright © 2015 American Chemical Society

Reprinted with permission from {Permselective Graphene Oxide Membrane for Highly Stable and Anti-Self-Discharge Lithium–Sulfur Batteries}. Copyright {2015} American Chemical Society.

A MnO2 functionalized Graphene/iMWCNT wrapped reduced diatomaceous earth anode will be made that will resemble this study that had an incredible 1525 mAh per gram capacity, high cycling stability and low resistance. The MnO2 functionalization will help recover some of the limited Li+ intercalation that graphene and iMWCNT are capable of.

A novel bath lily-like graphene sheet-wrapped nano-Si composite as a high performance anode material for Li-ion batteries

Yu-Shi He,a Pengfei Gao,a Jun Chen,b Xiaowei Yang,a Xiao-Zhen Liao,a Jun Yang*a and Zi-Feng Ma*a

Show Affiliations

RSC Adv., 2011,1, 958-960

DOI: 10.1039/C1RA00429H

First published online 07 Sep 2011

http://pubs.rsc.org/en/Content/ArticleLanding/2011/RA/C1RA00429H#!divAbstract

I will utilize microwave urea assisted reduction instead of calcining the composite at 700 degrees celcius. As is used in this study.

http://www.nmletters.org/articles-in-press/item/388-one-pot-microwave-assisted-synthesis-of-graphene-layered-double-hydroxide-ldh-nanohybrids

Sunil P. Lonkar, Jean-Marie Raquez, Philippe Dubois, "One-pot Microwave-assisted Synthesis of Graphene/Layered Double Hydroxide (LDH) Nanohybrids", Nano-Micro Lett. 7(3), - (2015). http://dx.doi.org/10.1007/s40820-015-0047-3

More information on microwave chemistry, the most powerful energy saving tool in the chemists arsenal.

http://digital.csic.es/bitstream/10261/78256/1/Microwave heating processes_JAMD_2010.pdf

I will continue to use chitosan as the binder my first results were very high resistance as I had a loading of around 29% whereas 8% by weight is sufficient. This was exhibited here. Used in a silicon anode an unheard of initial discharge capacity of 4270 mAh g was realized with a stable discharge of 950 mAh per gram thereafter.

http://www.sciencedirect.com/science/article/pii/S0378775313014237

Carboxymethyl chitosan: A new water soluble binder for Si anode of Li-ion batteries

• Lu Yuea, b,
• Lingzhi Zhanga, , ,
• Haoxiang Zhonga

• a CAS Key Laboratory of Renewable Energy, Guangzhou Institute of Energy Conversion, Chinese Academy of Sciences, Guangzhou, Guangdong 510640, China
• b University of Chinese Academy of Sciences, Beijing 100039, China

Received 17 June 2013, Revised 14 August 2013, Accepted 17 August 2013, Available online 5 September 2013

Another resource for microwave assisted calcination. I could use pre-calcined diatomaceous earth/kieselguhr but then I wont be synthesizing Silicon Carbide and increasing conductivity of the lithium containing silicon.

http://aceee.org/files/proceedings/2011/data/papers/0085-000086.pdf

Rapid Limestone Calcination Using Microwave Assist Technology Morgana Fall, Gibran Esquenazi, Shawn Allan and Holly Shulman, Ceralink Inc.

The Cathode

Metal organic framework, Asphaltenes which contain up to 7% sulfur themselves act as an incredible cathode material allowing adsorption of two lithium ions per sulfur atom. The problem is the Cathode would be too thick using asphaltenes alone as I need twice the number of atoms of sulfur to silicon to balance the electrodes(silicon can store 4 lithium ions as opposed to sulfur's 2). So I will have to add elemental sulfur, the procedure will be to ball mill the asphaltenes, graphene oxide and ox-iMWCNT together to create a nanowrapped sulfur allowing electron flow to the sulfur on discharge.

http://www.science20.com/news_articles/lithiumsulfur_batteries_with_a_graphene_wrapper-151830

Will update later sleep calls

Since Super-capacitors can only hold a theoretical 400mWh per gram a change has been needed I do not see them as viable when placed in a race with a lithium sulfur battery with a theoretical 2200mWh per gram and a proven capacity of up to 1300mWh per gram.

A Lithium Ion, Sulfur-Cathode, Silicon Anode battery has not been tried yet. The question is why has this not been tried? Silicon-Lithium batteries are made with nano-silicon wires pre doped with lithium in the Anode. Sulfur Lithium batteries are made with a Solid Lithium Anode and a Sulfur Cathode. Combining the two should allow a greater increase in performance.

Lithium-Sulfur batteries have a theoretical energy density of 2200mAh per gram, Lithium-Silicon batteries also have a theoretical energy density of 4200mAh per gram. Super Capacitors have an theoretical energy density of 200-400mWh per gram.

The idea now is to combine all three and reduce the lithium required to make the Ultra-capacitor by half of that of a normal battery.

In order to create the Anode a very high loading of Urea will be required to fully reduce the Kieselguhr (amorphous Silicon Dioxide SiO2) GO, oxIMWCNT and lithium hydroxide. Kieselguhr should provide a benefit over SiO2 nanowires in that its total surface are should be much higher. The benefit should remove the need for a binder as the anode will be highly cross linked. MnO2 addition will increase the lithium ion storage capability of the small amount of Carbon needed to facilitate electron flow to and from the reduced SiO2[1}. This electrode will be spun cast onto a stainless electrode and reduced in-situ via microwave assisted urea reduction. I will harvest the lithium from an energizer battery and convert it to hydroxide by placing it in water.

A reduced Graphene Oxide, oxiMWCNT secondary Anode will protect the Primary Silicon Anode from sulfating significantly increasing the lifespan[2]. This should also provide a layer that will demonstrate Psuedo-capacitance with a phosphoric acid/lithium ion electrolyte. A dodecylbenzene sulfonic acid seperator will be applied to the interspacial area between the secondary anode and the cathode, this will allow the psuedocapacitive double layer to avoid leakage while remaining permable to ion flow under normal conditions this has also not been tried. Ideally the psuedocapacitive effect should have the least resistance and discharge/charge first allowing surge power and surge charging to happen almost instantaneously. A crosslinked solid PVA borax electrolyte should provide enough support to keep the secondary anode from degrading do to ion swell during charging. The amount of borax needed is a large variable and will require much experimentation. This electrode will be drop cast upon glass containing an aluminum mesh screen, then reduced in-situ via microwave assisted urea reduction.

The cathode will be constructed with a majority of Asphaltenes as the 7% sulfur and 3% nitrogen loading as well as vanadium and nickel hemes will allow a large amount of lithium to be adsorbed upon discharge of the cell and will facilitate faster charge/discharge rates{3,6}. A small amount of partially reduced N Ox MWCNT will allow higher conductivity on the Cathode. A binder in the form of Chitosan will be required due to the small amount of reduction and subsequent cross linking of the Cathode. The chitosan will also sufficiently retain the sulfur in the cathode reducing the significant wear rate from sulfur migration seen in as to date lithium-sulfur batteries. This electrode will be partially solvated and dispersed in household vinegar drop then drop cast onto a stainless steel charge carrier. It will then be reduced via urea microwave assisted reduction in-situ

Ideally the electrolyte should be an ionic liquid to allow higher super, constructed with quaternary ammonium salts. However I have tried unsuccessfully to create one with cheap readily available materials, as the urea used to form the deep eutectic solvent degrades upon charging releasing ammonia and reducing oxygen functional groups. Hence the desire to go back to a solid PVA phosphoric electrolyte. The proposed plan is to simply harvest lithium salts from a worn out lithium ion battery. Cutting one apart was scary but it did proved a large portion of lithium salts scraped from the semi-permeable membrane separator.

The question remains to whether the lithium ions will be motile in this electrolyte. Only time can tell as literature does not specifically cover PVA as an organic solvent that allows efficient transfer of lithium ions. It works for phosphoric acid so it should for the Li+ ion. Another issue is whether or not try and use a copper charge collector on the anode as is widely used in lithium ion batteries do to its electronegativity and excess electrons.

1. Wu, Xiaomin; Li, Huan; Fei, Hailong; Zheng, Cheng; Wei, Mingdeng (2014). "Facile synthesis of Li2MnO3 nanowires for lithium-ion battery cathodes". New Journal of Chemistry 38: 584–587.
2. "Li-S battery company OXIS Energy reports 300 Wh/kg and 25 Ah cell, predicting 33 Ah by mid-2015, 500 Wh/kg by end of 2018". Green Car Congress. November 12, 2014. Retrieved February 2015.
3. https://en.wikipedia.org/wiki/Asphaltene Creative Commons Attribution-ShareAlike License.
   
4. https://en.wikipedia.org/wiki/Lithium–sulfur_battery Creative Commons Attribution-ShareAlike License.
   
5. https://en.wikipedia.org/wiki/Nanowire_battery#cite_note-23 Creative Commons Attribution-ShareAlike License.
   
6. American Vanadium Corp. "Lithium Vanadium Phosphate Battery". Retrieved 2013-10-22.

Pretty much all my updates will be on youtube from now on, I have made some new fibers and will get them up asap I had about 40 more problems since the last update but we are cruising back into territory I know my way around in the field of chemistry.

I had to rebuild my 3d printer it is a prusa I3 rework from ebay. I needed risers and a hopper printed for my filament extruder and what I had was just not cutting it. There were many broken parts as it was shipped rather haphazardly. It is rebuilt now and all axis are tight and moving.

I am looking at building a website to better host this information as there are alot of steps past getting the actual large production tools built, but I have tested all of this on a small scale and it works. If anyone has any idea as to the best place for free web hosting let me know.

I completed most of the extruder today, I simply need a 5/8 spade bit to finish it. Will complete tommorow, Still working on completing the first 3d printable end connector prototype in design spark mechanical. Picture is up.

My previous connectors were made with clay and molded with silicone and high temp resin, they looked like hell but were simply usefull to prove to myself this would work.

If you haven't used design spark you definitely need to check it out. http://www.rs-online.com/designspark/electronics/eng/page/mechanical its a free super simple cad program that is perfect for designing 3d printable objects.