Dubbed the Electric Highway, the network will, when completed in three months, allow EV drivers to travel from Exeter to Edinburgh via London without fear of running out of juice.
Further connections are planned for the next 18 months.
Both businesses expect to benefit from a unique synergy, where Welcome Break sees an opportunity to attract more custom to its motorway service stations, and Ecotricity is keen to find new markets in an emerging and potentially huge area.
Together, they hope to open up low-carbon transport routes to the whole of the UK - not just within cities.
Dale Vince, Ecotricity's founder, said: "Until now, charging posts have all been in city centres like London, but statistics show that it's not in towns and cities where electric cars need to recharge, but on longer journeys between cities - and that means motorways."
The first 'top-up zone' is being installed this month at Welcome Break's South Mimms services (at the Junction of the M1 and M25), and the first phase of the network spread across 12 motorway services will be completed by September.
Each post will be located outside the main entrance, with two sockets that can be accessed by registering for a free swipecard at the website ecotricity.co.uk/onthemove.
Within 18 months all 27 Welcome Break motorway services will have charging points.
The partnership claims that electric cars will be able to top-up in just 20 minutes using rapid recharge points (32A supply) or fully charge in two hours; while those using the slower (13A supply) will be able to recharge fully if staying overnight in adjoining hotels.
"We're creating the infrastructure to get Britain's electric car revolution moving," added Vince. "This marks the beginning of the end for the old combustion engine. With world oil prices going through the roof, you'll now be able to get around Britain using only the power of the wind. It costs 1p a mile in an electric vehicle, compared with 10p in a petrol car (at today's oil prices)."
A driver travelling a year's typical 12,000 miles could save almost lb2000 in petrol costs at today's prices, and around 2500kg in CO2 emissions.
Rod McKie, CEO of Welcome Break, spoke of his excitement at the project, and affirmed that the company "wants to be at the forefront" of the coming change in motoring habits: "as hybrid and electric cars become part of everyday life, Welcome Break will have the facility to fast-charge these cars, giving electric car drivers the opportunity to travel the length and breadth of the UK".
Ecotricity has also installed a charging post at its windmill next to the M4 motorway in Reading. It is the first charging post to be powered directly from a wind turbine.
"Video production: Tim Walter Associates"
In November 2010, Ecotricity launched the Nemesis, a wind-powered sports car that can reach 0-100mph in 8.5 seconds and with a top speed of 170mph. The first electric "supercar" to be designed and built in Britain, the Nemesis was created by an A-team of ex-Formula 1 engineers with the brief to "blow the socks off Jeremy Clarkson" and show that electric cars can be sexy, fast and fun to drive.
It will be the first electric car to drive from Land's End to John O' Groats this summer.
This year, major manufacturers are launching all-electric mass-market models including the Nissan Leaf, Mitsubishi MIEV and Peugeot iOn. Ford will also launch an all-electric version of its Ford Focus, on sale in 2013.
COULD WIND POWER REPLACE THE COMBUSTION ENGINE?
Dale Vince, long an evangelist for renewable electricity, asserts that "with 10,000 of today's wind turbines, or just 5,000 of tomorrow's" we could replace all of the "25 million barrels of oil" that we consume in the UK to travel "the 250 billion miles we drive every year."
His company has calculated that if all 30 million vehicles on the roads were replaced by EVs, which typically do 5,000 miles on one MWh of electricity, then the UK would need 13% - or 50TWh - more electricity to power those journeys than is currently generated.
Total UK grid demand was 378TWh in 2009, and a 13% increase in output is equal to just four years of annual demand growth, and to the output from 10,000 wind turbines (assuming their current design) - which would save 69 million tonnes of CO2 emissions annually.
However, as most EV charging is expected to happen overnight, when grid demand is traditionally lowest, this may not translate directly to a corresponding 13% increase in capacity.
But the revolution, if it is to happen, will take around a decade. There are currently only about 2,000 pure electric vehicles in the UK; on top of that there are a few hundred plug-in electric hybrids.
The 30,000 petrol hybrids on the roads that have a battery fitted cannot plug them into a socket; their charge either comes from the petrol engine or from energy stored during braking.
There are now around 400 charging points in cities around the UK, most of which - around 250 - are in London. But most charging is expected to happen overnight at home, with some to be offered at the workplace.
Dale Vince founded Ecotricity 15 years ago. A 'not for dividend' company with no shareholders, it now powers 50,000 homes and businesses in the UK from its fleet of 52 wind turbines, and invests more per capita in building new sources of green energy than any other UK electricity company. It is the only energy supplier supported by Oxfam and the Soil Association.
Welcome Break's 27 service areas house the firm's own brands alongside high-street names such as Burger King, KFC, WHSmith and Days Inn. Recently Waitrose and Starbucks have also been added.
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